Monomer having electron-withdrawing group and process for preparing the same

ABSTRACT

A monomer containing an electron-withdrawing group of the present invention is represented by following Formula (a), (b) or (c): 
                 
 
wherein A 1 , A 2 , and A 3  are each a ring; R a , R b , R c , and R u  are the same or different and are each a hydrogen atom or organic group; at least one of R s , R w  and R v , at least one of R t  and R w1 , and at least one of the two R w2 s are each an electron-withdrawing group, and the others are each a hydrogen atom or organic group; W 1  is a single bond or linkage group; and n denotes an integer of 2 to 25, where at least two of R a , R b , R c , R s , R t , R u , R v , R w , R w1 , R w2 , W 1 , and carbon atoms constituting ring A 1 , carbon atoms constituting ring A 2 , and carbon atoms constituting ring A 3  may be combined to form a ring, respectively. The electron-withdrawing groups in R s , R t , R v , R w , R w1 , and R w2  are, for example, groups each containing a fluorine atom. The monomer is useful as a raw material for photoresist polymeric compounds.

This application is the national phase under 35 U.S.C. § 371 of PCTInternational Application No. PCT/JP01/09530 which has an Internationalfiling date of Oct. 31, 2001, which designated the United States ofAmerica.

TECHNICAL FIELD

The present invention relates to novel monomers each containing anelectron-withdrawing group which are useful as monomers forphotosensitive resins and other functional polymers and processes forproducing the same, as well as to intermediates of the monomers eachcontaining an electron-withdrawing group and processes for producing thesame. In addition, it relates to polymeric compounds for use inphotoresists which can be obtained from the monomers each containing anelectron-withdrawing group, photosensitive resin compositions,patterning processes and processes for manufacturing semiconductors.

BACKGROUND ART

Compounds each having a bridged cyclic skeleton such as an adamantaneskeleton, 3-oxatricyclo[4.3.1.1^(4,8)]undecane skeleton analogous to theadamantane skeleton, norbornene skeleton,2-oxabicyclo[3.2.1^(1,5)]-6-octene skeleton analogous to the norborneneskeleton have three-dimensionally special ring systems. For example,these compounds are non-aromatic and rigid. These compounds cantherefore exhibit various functions and receive attention in the fieldsof, for example, photosensitive resins in which high performances arerequired. Separately, a fluorine atom can impart, owing to its electricproperties and other properties, special functions such as waterresistance, water repellency, chemical resistance, mechanical strength,and sliding property to molecules. Investigations on organic compoundscontaining fluorine atoms have therefore actively been made.

However, there are known only few polymerizable compounds having higherfunctions, which polymerizable compounds each contain a bridged cyclicskeleton, such as the adamantane skeleton, having a polymerizable groupwith a fluorine atom or a group containing a fluorine atom bondedthereto and have both the functions of the bridged cyclic skeleton andthe functions of the fluorine atom. In addition to these compounds,cyclic compounds each having an electron-withdrawing group such as agroup containing a fluorine atom and being polymerizable have highfunctions and receive attention specifically in the field ofphotosensitive resins. Expectations with respect to novel monomers eachcontaining an electron-withdrawing group thereby grow.

Additionally, demands have been made on polymeric compounds for use inphotoresists, photosensitive resin compositions, patterning processes,and processes for manufacturing semiconductors, which can highlyprecisely form finer patterns.

DISCLOSURE OF INVENTION

Accordingly, an object of the present invention is to provide a novelmonomer having a cyclic skeleton and containing an electron-withdrawinggroup and a polymerizable group, as well as to provide a process forproducing the same.

Another object of the present invention is to provide a novelpolymerizable bridged cyclic compound (monomer) containing a fluorineatom, which includes a bridged cyclic skeleton, such as an adamantaneskeleton, and a group containing a fluorine atom bonded to the skeletonand has a polymerizable group, as well as to provide a process forproducing the same.

A further object of the present invention is to provide an intermediatethat is useful in production of the novel monomer having a cyclicskeleton, as well as to provide a process for producing theintermediate.

In addition, another object of the present invention is to provide apolymeric compound for use in photoresists, a photosensitive resincomposition, a patterning process, and a process for manufacturing asemiconductor which can highly precisely form very fine patterns.

After intensive investigations to achieve the above objects, the presentinventors have successfully synthesized novel monomers each containingan electron-withdrawing group, which include a cyclic group such as anadamantane skeleton or 3-oxatricyclo[4.3.1.1^(4,8)]undecane skeleton andan electron-withdrawing group, such as a group containing a fluorineatom, bonded to the cyclic group and have an ethylenic double bond. Inaddition, they have found that the monomers each containing anelectron-withdrawing group can yield polymeric compounds for use inphotoresists exhibiting high sensitivity. The present invention has beenaccomplished based on these findings.

Specifically, the present invention provides a monomer containing anelectron-withdrawing group, represented by following Formula (a), (b) or(c):

wherein A¹, A², and A³ are each a ring; R^(a), R^(b), R^(c), and R^(u)are the same or different and are each a hydrogen atom or an organicgroup; at least one of R^(s), R^(w) and R^(v), at least one of R^(t) andR^(w1), and at least one of the two R^(w2)s are each anelectron-withdrawing group, and the others are each a hydrogen atom oran organic group; W¹ is a single bond or a linkage group; and n denotesan integer of from 2 to 25, where at least two of R^(a), R^(b), R^(c),R^(s), R^(t), R^(u), R^(v), R^(w), R^(w1), R^(w2), W¹, and carbon atomsconstituting ring A¹, carbon atoms constituting ring A², and carbonatoms constituting ring A³ may be combined to form a ring, respectively.

The electron-withdrawing groups in R^(s), R^(t), R^(v), R^(w), R^(w1),and R^(w2) include, for example, groups each containing a fluorine atom.Ring A¹, ring A² or ring A³ may for example be a monocyclic ring orbridged ring containing at least a 5- to 7-membered carbocyclic ring oroxygen-containing heterocyclic ring. The monomer containing anelectron-withdrawing group may have a bridged ring skeleton includingring A¹, ring A² or ring A³ and containing 7 to 15 carbon atoms.

The present invention also provides a process for producing a monomercontaining an electron-withdrawing group. The process includes the stepof allowing a cyclic ketone having an ethylenic double bond, representedby following Formula (d):

wherein A² is a ring; R^(a), R^(b), R^(c) and R^(u) are the same ordifferent and are each a hydrogen atom or an organic group; W¹ is asingle bond or a linkage group; and n denotes an integer of from 2 to25, where at least two of R^(a), R^(b), R^(c), R^(u), W¹, and carbonatoms constituting ring A² may be combined to form a ring, respectively,to react with a fluorine reagent, or subjecting the cyclic ketone havingan ethylenic double bond represented by Formula (d) to a reaction withthe fluorine reagent and to a subsequent reaction for introducing aprotecting group to thereby yield a monomer containing a fluorine atomand having an ethylenic double bond, represented by following Formula(b1):

wherein R^(x) is a group containing a fluorine atom; R^(d) is a hydrogenatom or a hydroxyl-protecting group; A², R^(a), R^(b), R^(c), R^(u), W¹,and n have the same meanings as defined above, where at least two ofR^(a), R^(b), R^(c), R^(u), W¹, and carbon atoms constituting ring A maybe combined to form a ring, respectively.

The present invention further provides a process for producing a monomercontaining an electron-withdrawing group. The process includes the stepof allowing a cyclic thioester having an ethylenic double bond,represented by following Formula (e):

wherein A³ is a ring; R^(a), R^(b), R^(c), and R^(u) are the same ordifferent and are each a hydrogen atom or an organic group; W¹ is asingle bond or a linkage group; and n denotes an integer of from 2 to25, where at least two of R^(a), R^(b), R^(c), R^(u), W¹, and carbonatoms constituting ring A³ may be combined to form a ring, respectively,to react with a fluorine reagent to thereby yield a monomer containing afluorine atom and having an ethylenic double bond, represented byfollowing Formula (c1):

wherein R^(x), R^(y1) are each a group containing a fluorine atom; A³,R^(a), R^(b), R^(c), R^(u), W¹, and n have the same meanings as definedabove, where at least two of R^(a), R^(b), R^(c), R^(u), W¹, and carbonatoms constituting ring A³ (maybe combined to form a ring, respectively.

In addition, the present invention provides the monomer having a cyclicthioester skeleton represented by Formula (e) The monomers eachcontaining an electron-withdrawing group of the present inventioninclude a compound represented by following Formula (1):

wherein R^(a), R^(b), and R^(c) are the same or different and are each ahydrogen atom or an organic group, where R^(a) and R^(b) may be combinedto form a ring with the adjacent carbon atom; Z is a single bond or anoxygen atom; R^(x) is a group containing a fluorine atom and R^(y) is a—OR^(d) group, where R^(d) is a hydrogen atom or a hydroxyl-protectinggroup, when Z is a single bond; R^(x) and R^(y) are each a groupcontaining a fluorine atom when Z is an oxygen atom, where carbon atomsconstituting the ring in the formula may each have a substituent.

The present invention also provides a process for producing a monomercontaining an electron-withdrawing group. The process includes the stepof allowing an adamantanone derivative having an ethylenic double bond,represented by following Formula (2):

wherein R^(a), R^(b), and R^(c) are the same or different and are each ahydrogen atom or an organic group, where R^(a) and R^(b) may be combinedto form a ring with the adjacent carbon atom, and carbon atomsconstituting the ring in the formula may each have a substituent, toreact with a fluorine reagent, or subjecting the adamantanone derivativehaving an ethylenic double bond represented by Formula (2) to a reactionwith a fluorine reagent and to a subsequent reaction for introducing aprotecting group to thereby yield an adamantane derivative containing afluorine atom and having an ethylenic double bond, represented byfollowing Formula (1a):

wherein R^(a), R^(b), and R^(c) have the same meanings as defined above;R^(d) is a hydrogen atom or a hydroxyl-protecting group; and R^(x) is agroup containing a fluorine atom, where carbon atoms constituting thering in the formula may each have a substituent.

The present invention further provides a process for producing a monomercontaining an electron-withdrawing group. The process includes the stepof allowing an 3-oxatricyclo[4.3.1.1^(4,8)]undecane-2-thione derivativehaving an ethylenic double bond, represented by following Formula (3a):

wherein R^(a), R^(b), and R^(c) are the same or different and are each ahydrogen atom or an organic group, where R^(a) and R^(b) may be combinedto form a ring with the adjacent carbon atom, and carbon atomsconstituting the ring in the formula may each have a substituent, toreact with a fluorine reagent to thereby yield an3-oxatricyclo[4.3.1.1^(4,8)]undecane derivative containing a fluorineatom and having an ethylenic double bond, represented by followingFormula (1b):

wherein R^(a), R^(b), and R^(c) have the same meanings as defined above;and R^(x) and R^(y1) are each a group containing a fluorine atom, wherecarbon atoms constituting the ring in the formula may each have asubstituent.

The present invention also provides the adamantanone derivative havingan ethylenic double bond represented by Formula (2).

The present invention further provides an3-oxatricyclo[4.3.1.1^(4,8)]undecane derivative having an ethylenicdouble bond, represented by following Formula (3):

wherein Y¹ is an oxygen atom or a sulfur atom; and R^(a), R^(b), andR^(c) are the same or different and are each a hydrogen atom or anorganic group, where R^(a) and R^(b) may be combined to form a ring withthe adjacent carbon atom, and carbon atoms constituting the ring in theformula may each have a substituent.

In addition, the present invention provides a process for producing an3-oxatricyclo[4.3.1.1^(4,8)]undecane-2-thione derivative. The processincludes the step of allowing an3-oxatricyclo[4.3.1.1^(4,8)]undecan-2-one derivative having an ethylenicdouble bond, represented by following Formula (3b):

wherein R^(a), R^(b), and R^(c) are the same or different and are each ahydrogen atom or an organic group, where R^(a) and R^(b) may be combinedto form a ring with the adjacent carbon atom, and carbon atomsconstituting the ring in the formula may each have a substituent, toreact with a sulfurizing agent to thereby yield the3-oxatricyclo[4.3.1.1^(4,8)]undecane-2-thione derivative having anethylenic double bond represented by Formula (3a).

The present invention also provides a process for producing a bridgedcyclic compound having an ethylenic double bond. The process includesthe step of subjecting a bridged cyclic compound containing ahydroxyalkyl group, represented by following Formula (4):

wherein R^(a), R^(b), and R^(c) are the same or different and are each ahydrogen atom or an organic group, where R^(a) and R^(b) may be combinedto form a ring with the adjacent carbon atom; and Z is a single bond oran oxygen atom, where carbon atoms constituting the ring in the formulamay each have a substituent, to a dehydration reaction to thereby yielda bridged cyclic compound having an ethylenic double bond, representedby following Formula (5):

wherein R^(a), R^(b), and R^(c) have the same meanings as defined above;and Z is a single bond or an oxygen atom, where carbon atomsconstituting the ring in the formula may each have a substituent.

The present invention also provides the bridged cyclic compoundcontaining a hydroxyalkyl group represented by Formula (4).

The present invention further provides a process for producing a bridgedcyclic compound containing a hydroxyalkyl group. The process includesthe step of subjecting a bridged cyclic compound containing an acylgroup, represented by following Formula (6):

wherein R^(a) and R^(b) are the same or different and are each ahydrogen atom or an organic group, where R^(a) and R^(b) may be combinedto form a ring with the adjacent carbon atom; and Z is a single bond oran oxygen atom, where carbon atoms constituting the ring in the formulamay each have a substituent, to reduction or to a reaction with anorganometallic compound represented by following Formula (9):R^(c1)-M  (9)wherein R^(c1) is an organic group; and M is a metallic atom which mayhave a ligand or a group represented by following Formula (10):—MgX¹  (10)wherein X¹ is a halogen atom,to thereby yield the bridged cyclic compound containing a hydroxyalkylgroup represented by Formula (4).

The present invention also provides the bridged cyclic compoundcontaining an acyl group represented by Formula (6).

In addition, the present invention provides a process for producing abridged cyclic compound containing an acyl group. The process includesthe step of allowing a bridged cyclic compound represented by followingFormula (7):

wherein Z is a single bond or an oxygen atom, and carbon atomsconstituting the ring in the formula may each have a substituent, whereat least one of the carbon atoms carries a hydrogen atom bonded thereto,to react with an acylating agent comprising (A) a 1,2-dicarbonylcompound or its hydroxy reductant represented by following Formula (8):

wherein R^(a), R^(b) and R are the same or different and are each ahydrogen atom or an organic group, where R^(a) and R^(b) may be combinedto form a ring with the adjacent carbon atom; and Z¹ and Z² are the sameor different and are each an oxygen atom or a hydroxyl group,(B) oxygen, and (C) at least one compound selected from (c1) metalliccompounds and (c2) N-hydroxy or N-oxo cyclic imide compounds, to therebyyield the bridged cyclic compound containing an acyl group representedby Formula (6).

The present invention further provides a process for producing a monomercontaining an electron-withdrawing group. The process includes the stepof allowing a cyclic compound containing an acyl group and having anethylenic double bond, represented by following Formula (f):

wherein A¹ is a ring; R^(a), R^(b), R^(c), and R^(e) are the same ordifferent and are each a hydrogen atom or an organic group; W¹ is asingle bond or a linkage group, where at least two of R^(a), R^(b),R^(c), R^(e), W¹, and carbon atoms constituting ring A¹ may be combinedto form a ring, respectively,to react with a fluorine reagent, or subjecting the cyclic compoundcontaining an acyl group and having an ethylenic double bond representedby formula (f) to a reaction with the fluorine reagent and to asubsequent reaction for introducing a protecting group, to thereby yielda polymerizable cyclic compound containing a fluorine atom and having anethylenic double bond, represented by following Formula (a1):

wherein R^(z) is a group containing a fluorine atom; R^(f) is a hydrogenatom or a hydroxyl-protecting group; and A¹, R^(a), R^(b), R^(c), R^(e),and W¹ have the same meanings as defined above, where at least two ofR^(a), R^(b), R^(c), R^(e), W¹, and carbon atoms constituting ring A¹may be combined to form a ring, respectively.

The monomers each containing an electron-withdrawing group of thepresent invention also include a compound represented by followingFormula (12):

wherein R^(a), R^(b), R^(c), and R^(e) are the same or different and areeach a hydrogen atom or an organic group, where R^(a) and R^(b) may becombined to form a ring with the adjacent carbon atom; R^(f) is ahydrogen atom or a hydroxyl-protecting group; and R^(z) is a groupcontaining a fluorine atom, where carbon atoms constituting the ring inthe formula may each have a substituent.

In addition, the present invention provides a process for producing amonomer containing an electron-withdrawing group. The process includesthe step of allowing an acyladamantane derivative having an ethylenicdouble bond, represented by following Formula (13):

wherein R^(a), R^(b), R^(c), and R^(e) are the same or different and areeach a hydrogen atom or an organic group, where R^(a) and R^(b) may becombined to form a ring with the adjacent carbon atom, and carbon atomsconstituting the ring in the formula may each have a substituent,to react with a fluorine reagent, or subjecting the acyladamantanederivative having an ethylenic double bond represented by Formula (13)to a reaction with the fluorine reagent and to a subsequent reaction forintroducing a protecting group, to thereby yield the adamantanederivative containing a fluorine atom and having an ethylenic doublebond represented by Formula (12).

The present invention further provides a process for producing a bridgedcyclic compound containing an acyl group. The process includes the stepof allowing an adamantane derivative having an ethylenic double bond,represented by following Formula (14):

wherein R^(a), R^(b), and R^(c) are the same or different and are each ahydrogen atom or an organic group, where R^(a) and R^(b) may be combinedto form a ring with the adjacent carbon atom, and carbon atomsconstituting the ring in the formula may each have a substituent, toreact with an acylating agent comprising (A1) a 1,2-dicarbonyl compoundor its hydroxy reductant represented by following Formula (15):

wherein R^(e) and R are the same or different and are each a hydrogenatom or an organic group; and Z¹ and Z² are the same or different andare each an oxygen atom or a hydroxyl group,(B) oxygen, and (C) at least one compound selected from (c1) metalliccompounds and (c2) N-hydroxy or N-oxo cyclic imide compounds, to therebyyield the acyladamantane derivative having an ethylenic double bondrepresented by Formula (13).

In addition, the present invention provides the acyladamantanederivative having an ethylenic double bond represented by Formula (13).

The monomers each containing an electron-withdrawing group of thepresent invention further include a compound represented by followingFormula (16):

wherein Z is a single bond or an oxygen atom; R^(x) is a groupcontaining a fluorine atom and R^(y) is a —OR^(d) group, where R^(d) isa hydrogen atom or a hydroxyl-protecting group, when Z is a single bond;and R^(x) and R^(y) are each a group containing a fluorine atom when Zis an oxygen atom, where carbon atoms constituting the ring in theformula may each have a substituent.

The monomers each containing an electron-with drawing group of thepresent invention also include a compound represented by followingFormula (17):

wherein R^(e) is a hydrogen atom or an organic group; R^(f) is ahydrogen atom or a hydroxyl-protecting group; and R^(z) is a groupcontaining a fluorine atom, where carbon atoms constituting the ring inthe formula may each have a substituent.

In addition, the present invention provides a monomer containing anelectron-withdrawing group, represented by following Formula (g), (h),(i) or (j):

wherein A⁴, A⁵, A⁶, and A⁷ are each a ring; R^(a), R^(b), R^(c), andR^(u) are the same or different and are each a hydrogen atom or anorganic group; at least one of R^(s), R^(w), and R^(v) in Formula (g),at least one of the two R^(w2)s in Formula (h), at least one of the twoR^(w3)s in Formula (i), and at least one of the four R^(w4)s in Formula(j) are each an electron-withdrawing group, and the others are each ahydrogen atom or an organic group; W¹ is a single bond or a linkagegroup; W² is a linkage group; n denotes an integer of from 2 to 25; m1and m2 are each an integer of from 0 to 2; G¹, G³, G⁴, and G⁵ are each alinkage group comprising a hetero atom; G² is a single bond or a linkagegroup comprising a hetero atom, where G² is a linkage group comprising ahetero atom when G¹ is an oxygen atom; at least two of R^(a), R^(b),R^(c), R^(s), R^(u), R^(v), R^(w), R^(w2), R^(w3), R^(w4), W¹, W²,carbon atoms constituting ring A⁴, carbon atoms constituting ring A⁵,carbon atoms constituting ring A⁶, and carbon atoms constituting ring A⁷may be combined to form a ring, respectively.

The electron-withdrawing groups in R^(s), R^(v), R^(w), R^(w2), R^(w3),and R^(w4) include, for example, groups each containing a fluorine atom.Ring A⁴ or ring A⁵ may for example be a monocyclic ring or bridged ringcontaining at least a 5- to 7-membered carbocyclic ring, a 5- to7-membered oxygen-containing heterocyclic ring or a 5- to 7-memberedsulfur-containing heterocyclic ring. The monomers containing anelectron-withdrawing group may have a bridged cyclic skeleton includingring A⁴ or ring A⁵ and containing 7 to 15 carbon atoms. In the monomerscontaining an electron-withdrawing group, ring A⁶ or ring A⁷ may be a 5-or 6-membered oxygen-containing heterocyclic ring or a 5- or 6-memberedsulfur-containing heterocyclic ring.

The present invention further provides a process for producing a monomercontaining an electron-withdrawing group. The process includes the stepof allowing a compound containing an acyl group and having an ethylenicdouble bond, represented by following Formula (k):

wherein A⁴ is a ring; R^(a), R^(b), R^(c), and R^(e) are the same ordifferent and are each a hydrogen atom or an organic group; W¹ is asingle bond or a linkage group; W² is a linkage group, where at leasttwo of R^(a), R^(b), R^(c), R^(e), W¹, W², and carbon atoms constitutingring A⁴ may be combined to form a ring, respectively,to react with a fluorine reagent, or subjecting the cyclic compoundcontaining an acyl group and having an ethylenic double bond representedby Formula (k) to a reaction with the fluorine reagent and to asubsequent reaction for introducing a protecting group, to thereby yielda monomer containing a fluorine atom and having an ethylenic doublebond, represented by following Formula (g1):

wherein R^(z) is a group containing a fluorine atom; R^(f) is a hydrogenatom or a hydroxyl-protecting group; and A⁴, R^(a), R^(b), R^(c), R^(e),W¹, and W² have the same meanings as defined above, where at least twoof R^(a), R^(b), R^(c), R^(e), W¹, W², and carbon atoms constitutingring A⁴ may be combined to form a ring, respectively.

Furthermore, the present invention provides a process for producing amonomer containing an electron-withdrawing group. The process includesthe step of allowing a cyclic compound containing a hydroxyl group or amercapto group and having an ethylenic double bond, represented byfollowing Formula (1):

wherein A⁴ is a ring; R^(a), R^(b), and R^(c) are the same or differentand are each a hydrogen atom or an organic group; W¹ is a single bond ora linkage group; W^(2a) is an oxygen atom or a sulfur atom, where atleast two of R^(a), R^(b), R^(c), W¹, and carbon atoms constituting ringA⁴ may be combined to form a ring, respectively, to react with acarbonyl compound containing a fluorine atom, represented by followingFormula (m):

wherein R^(w5) is a group containing a fluorine atom, or subjecting thecyclic compound containing a hydroxyl group or a mercapto group andhaving an ethylenic double bond represented by Formula (1) to a reactionwith the carbonyl compound containing a fluorine atom represented byFormula (m) and to a subsequent reaction for introducing a protectinggroup, to thereby yield a monomer containing a fluorine atom and havingan ethylenic double bond, represented by following Formula (g2):

wherein R^(f) is a hydrogen atom or a hydroxyl-protecting group; A⁴,R^(a), R^(b), R^(c), R^(w5), W¹, and W² have the same meanings asdefined above, where at least two of R^(a), R^(b), R^(c), W¹, and carbonatoms constituting ring A⁴ may be combined to form a ring, respectively.

The monomers each containing an electron-with drawing group of thepresent invention also include a compound represented by followingFormula (18):

wherein R^(e) is a hydrogen atom or an organic group; W² is a linkagegroup; R^(f) is a hydrogen atom or a hydroxyl-protecting group; andR^(z) is a group containing a fluorine atom, where carbon atomsconstituting the ring in the formula may each have a substituent.

In addition, the present invention provides a process for producing amonomer containing an electron-withdrawing group. This process includesthe step of allowing a cyclic compound containing a thiocarbonyl groupand having an ethylenic double bond, represented by following Formula(n):

wherein A⁵ is a ring; R^(a), R^(b), R^(c), and R^(u) are the same ordifferent and are each a hydrogen atom or an organic group; W¹ is asingle bond or a linkage group; n denotes an integer of from 2 to 25; G¹is a linkage group comprising a hetero atom; and G² is a single bond ora linkage group comprising a hetero atom, where G² is a linkage groupcomprising a hetero atom when G¹ is an oxygen atom, and at least two ofR^(a), R^(b), R^(c), R^(u), W¹, and carbon atoms constituting ring A⁵may be combined to form a ring, respectively, to react with a fluorinereagent to thereby yield a monomer containing a fluorine atom and havingan ethylenic double bond, represented by following Formula (h1):

wherein R^(x) and R^(y1) are each a group containing a fluorine atom;and A⁵, R^(a), R^(b), R^(c), R^(u), W¹, n, G¹, and G² have the samemeanings as defined above, where at least two of R^(a), R^(b), R^(c),R^(u), W¹, and carbon atoms constituting ring A⁵ may be combined to forma ring, respectively.

The monomers each containing an electron-withdrawing group of thepresent invention further include a compound represented by followingFormula (19):

wherein R^(x) and R^(y1) are each a group containing a fluorine atom; G¹is a linkage group comprising a hetero atom; and G² is a single bond ora linkage group comprising a hetero atom, where G² is a linkage groupcomprising a hetero atom when G¹ is an oxygen atom, and carbon atomsconstituting the ring in the formula may each have a substituent.

The monomers each containing an electron-withdrawing group of thepresent invention also include a compound represented by followingFormula (20):

wherein R^(x) and R^(y1) are each a group containing a fluorine atom;R^(u) is a hydrogen atom or an organic group; G¹ is a linkage groupcomprising a hetero atom, where carbon atoms constituting the ring inthe formula may each have a substituent.

In addition, the present invention provides a process for producing amonomer containing an electron-withdrawing group. The process includesthe step of allowing a cyclic compound containing a thiocarbonyl groupand having an ethylenic double bond, represented by following Formula(o):

wherein A⁶ is a ring; R^(a), R^(c), and R^(u) are the same or differentand are each a hydrogen atom or an organic group; m1 and m2 are each aninteger of from 0 to 2; G³ and G⁴ are each a linkage group comprising ahetero atom, where at least two of R^(a), R^(c), R^(u), and carbon atomsconstituting ring A⁶ may be combined to form a ring, respectively,to react with a fluorine reagent to thereby yield a monomer containing afluorine atom and having an ethylenic double bond, represented byfollowing Formula (i1):

wherein R^(x) and R^(y1) are each a group containing a fluorine atom;A⁶, R^(a), R^(c), R^(u), m1, m2, G³, and G⁴ have the same meanings asdefined above, where at least two of R^(a), R^(c), R^(u), and carbonatoms constituting ring A⁶ may be combined to form a ring, respectively.

Additionally, the present invention provides a process for producing amonomer containing an electron-withdrawing group. The process includesthe step of allowing a cyclic compound containing a thiocarbonyl groupand having an ethylenic double bond, represented by following Formula(p):

wherein A⁷ is a ring; R^(a), R^(c), and R^(u) are the same or differentand are each a hydrogen atom or an organic group; m1 and m2 are each aninteger of from 0 to 2; and G⁵ is a linkage group comprising a heteroatom, where at least two of R^(a), R^(c), R^(u), and carbon atomsconstituting ring A⁷ may be combined to form a ring, respectively,to react with a fluorine reagent to thereby yield a monomer containing afluorine atom and having an ethylenic double bond, represented byfollowing Formula (j1):

wherein R^(x) and R^(y1) are each a group containing a fluorine atom;and A⁷, R^(a), R^(c), R^(u), m1, m2, and G⁵ have the same meanings asdefined above, where at least two of R^(a), R^(c), R^(u), and carbonatoms constituting ring A⁷ may be combined to form a ring, respectively.

The monomers each containing an electron-withdrawing group of thepresent invention also include a compound represented by followingFormula (21):

wherein R^(x) and R^(y1) are each a group containing a fluorine atom;and G³ and G⁴ are each a linkage group comprising a hetero atom, wherecarbon atoms constituting the ring in the formula may each have asubstituent.

The monomers each containing an electron-withdrawing group of thepresent invention also include a compound represented by followingFormula (22):

wherein R^(x) and R^(y1) are each a group containing a fluorine atom;and G⁵ is a linkage group comprising a hetero atom, where carbon atomsconstituting the ring in the formula may each have a substituent.

In addition, the present invention provides a polymeric compound for usein photoresists. The polymeric compound includes at least one ofconstitutional repeating units represented by following Formula (G),(H), (I), or (J):

wherein A⁴, A⁵, A⁶, and A⁷ are each a ring; R^(a), R^(b), R^(c), andR^(u) are the same or different and are each a hydrogen atom or anorganic group; at least one of R^(s), R^(w), and R^(v) in Formula (G),at least one of the two R^(w2)s in Formula (H), at least one of the twoR^(w3)s in Formula (I), and at least one of the four R^(w4)s in Formula(J) are each an electron-withdrawing group, and the others are each ahydrogen atom or an organic group; W¹ is a single bond or a linkagegroup; W² is a linkage group; n denotes an integer of from 2 to 25; m1and m2 are each an integer of from 0 to 2; G¹, G³, G⁴, and G⁵ are each alinkage group comprising a hetero atom; G² is a single bond or a linkagegroup comprising a hetero atom, where G² is a linkage group comprising ahetero atom when G¹ is an oxygen atom; at least two of R^(a), R^(b),R^(c), R^(s), R^(u), R^(v), R^(w), R^(w2), R^(w3), R^(w4), W¹, W² carbonatoms constituting ring A⁴, carbon atoms constituting ring A⁵, carbonatoms constituting ring A⁶, and carbon atoms constituting ring A⁷ may becombined to form a ring, respectively.

The present invention further provides a photosensitive resincomposition including at least the polymeric compound for use inphotoresists and a photosensitive acid generator.

In addition, the present invention provides a patterning processincluding at least the steps of applying the photosensitive resincomposition to a substrate, applying light with a wavelength of lessthan or equal to 220 nm, baking, and developing. As the light for useherein, F₂ excimer laser light can be used.

In addition and advantageously, the present invention provides a processfor manufacturing a semiconductor. The process includes the step ofpatterning according to the aforementioned patterning process.

In the present description, the term “monomer” means a startingsubstance which is used in the formation of a polymer by polymerizationreaction and is a constitutional unit compound of the polymer. The term“organic group” is used in a broad meaning including groups containingnon-metallic atoms, such as halogen atoms, hydroxyl group, mercaptogroup, amino group, nitro group, and sulfonic acid groups, in additionto groups containing carbon atoms. The term “group containing a fluorineatom” also includes a fluorine atom. The “hydroxyl-protecting group” in,for example, R^(d) means a functional group that can be derived from ahydroxyl group and also includes groups that are hardly deprotected, inaddition to groups that can easily be deprotected. The term “fluorinereagent” means a reagent that can introduce not only a fluorine atom butalso a group containing a fluorine atom in a broad meaning, such astrifluoromethyl group.

BEST MODE FOR CARRYING OUT THE INVENTION

[Monomers Containing an Electron-withdrawing Group]

The monomers each containing an electron-withdrawing group of thepresent invention are represented by Formula (a), (b) or (c). They alsoinclude the monomers represented by Formula (g), (h), (i) or (j).

In the monomers (polymerizable cyclic compounds) each containing anelectron-withdrawing group represented by Formula (a), ring A¹ ispreferably a non-aromatic carbocyclic ring or heterocyclic ring, ofwhich a non-aromatic carbocyclic ring and a non-aromaticoxygen-atom-containing heterocyclic ring are typically preferred. Suchnon-aromatic carbocyclic rings include, but are not limited to,cyclopentane ring, cyclohexane ring, cyclohexene ring, cycloheptanering, cyclooctane ring, cyclodecane ring, cyclododecane ring, and othermonocyclic rings; adamantane ring, norbornane ring, norbornene ring,decalin ring, perhydroindene ring, perhydrofluorene ring,perhydroanthracene ring, tricyclo[5.2.1.0^(2,6)]decane ring,tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodecane ring, and other bridgedrings. Such non-aromatic oxygen-atom-containing heterocyclic ringsinclude, but are not limited to, 3-oxatricyclo[4.3.1.1^(4,8)]undecanering, 2-oxabicyclo[3.2.1^(1,5)]octane ring,3-oxabicyclo[3.2.1^(1,5)]octane ring, 2-oxabicyclo[2.2.2^(1,4)]]octanering, and 6-oxatricyclo[3.2.1.1^(3,8)]nonane ring. Ring A¹ may have asubstituent. Such substituents include similar groups to substituentswhich the undermentioned organic groups or hydrocarbon groups may have.

R^(a), R^(b), and R^(c) are the same or different and are each ahydrogen atom or an organic group. Such organic groups are notspecifically limited and include, for example, hydrocarbon groups,heterocyclic groups, halogen atoms, alkoxycarbonyl groups,aryloxycarbonyl groups, acyl groups, cyano group, and nitro group.

The hydrocarbon groups include aliphatic hydrocarbon groups, alicyclichydrocarbon group, and aromatic hydrocarbon groups. Such aliphatichydrocarbon groups include, but are not limited to, methyl, ethyl,propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl,octyl, decyl, tetradecyl, hexadecyl, octadecyl, allyl, and otherstraight- or branched-chain aliphatic hydrocarbon groups (alkyl groups,alkenyl groups, and alkynyl groups) each containing from about 1 toabout 20 carbon atoms. Among them, those having from about 1 to about 10carbon atoms are preferred, of which those having from about 1 to about6 carbon atoms are typically preferred. The alicyclic hydrocarbon groupsinclude, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, cyclohexenyl, cyclooctyl, cyclodecyl, cyclododecyl, andother alicyclic hydrocarbon groups (e.g., cycloalkyl groups andcycloalkenyl groups) each containing from about 3 to about 20 carbonatoms, of which those containing from about 3 to about 15 carbon atomsare preferred. The aromatic hydrocarbon groups include, but are notlimited to, phenyl, naphthyl, and other aromatic hydrocarbon groups eachcontaining from about 6 to about 14 carbon atoms.

These hydrocarbon groups may have substituents. Such substituentsinclude, but are not limited to, halogen atoms (fluorine, chlorine,bromine, and iodine atoms), oxo group, hydroxyl group which may beprotected by a protecting group, hydroxymethyl group which may beprotected by a protecting group, amino group which may be protected by aprotecting group, carboxyl group which may be protected by a protectinggroup, substituted oxycarbonyl groups, substituted or unsubstitutedcarbamoyl groups, nitro group, acyl groups, cyano group, alkyl groups(e.g., methyl, ethyl, and other C₁-C₄ alkyl groups), cycloalkyl groups,aryl groups (e.g., phenyl and naphthyl groups), and heterocyclic groups.As the protecting groups, conventional protecting groups in the field oforganic synthesis can be used. Typical examples of hydrocarbon groupseach having a substituent are chloromethyl group, trifluoromethyl group,and other halogenated hydrocarbon groups.

Heterocyclic rings constituting the heterocyclic groups include aromaticheterocyclic rings and non-aromatic heterocyclic rings. Suchheterocyclic rings include, but are not limited to, heterocyclic ringseach containing an oxygen atom as a hetero atom (e.g., furan,tetrahydrofuran, oxazole, isoxazole, and other 5-membered rings,4-oxo-4H-pyran, tetrahydropyran, morpholine, and other 6-membered rings,benzofuran, isobenzofuran, 4-oxo-4H-chromene, chroman, isochroman, andother condensed rings), heterocyclic rings each containing a sulfur atomas a hetero atom (e.g., thiophene, thiazole, isothiazole, thiadiazole,and other 5-membered rings, 4-oxo-4H-thiopyran and other 6-memberedrings, benzothiophene and other condensed rings), heterocyclic ringseach containing a nitrogen atom as a hetero atom (e.g., pyrrole,pyrrolidine, pyrazole, imidazole, triazole, and other 5-membered rings,pyridine, pyridazine, pyrimidine, pyrazine, piperidine, piperazine, andother 6-membered rings, indole, indoline, quinoline, acridine,naphthyridine, quinazoline, purine, and other condensed rings). Theseheterocyclic groups may have substituents such as the substituents whichthe hydrocarbon groups may have.

The halogen atoms include fluorine, chlorine, bromine, and iodine atoms.The alkoxycarbonyl groups include, but are not limited to,methoxycarbonyl group and ethoxy carbonyl group. The aryloxycarbonylgroups include, for example, phenyloxycarbonyl group. The acyl groupsinclude, but are not limited to, formyl group, acetyl group, propionylgroup, and benzoyl group.

Preferred R^(a), R^(b), and R^(c) include, for example, hydrogen atom;methyl, ethyl, propyl, isopropyl, butyl, and other C₁-C₁₀ aliphatichydrocarbon groups (specifically, C₁-C₄ alkyl groups); alicyclichydrocarbon groups (especially, C₃-C₁₅ cycloalkyl groups or cycloalkenylgroups); C₆-C₁₄ aryl groups; trifluoromethyl group and other halogenatedhydrocarbon groups; fluorine atom, chlorine atom, and other halogenatoms.

At least one of R^(s), R^(w) and R^(v), at least one of R^(t) andR^(w1), and at least one of the two R^(w2)s are each anelectron-withdrawing group, and the others are each a hydrogen atom oran organic group.

Such electron-withdrawing groups include, but are not limited to,fluorine atom and other halogen atoms, trifluoromethyl group and otherhalogenated hydrocarbon groups, methoxycarbonyl group and otheralkoxycarbonyl groups, phenoxycarbonyl group and other aryloxycarbonylgroups, acetyl group and other acyl groups, cyano group, aryl groups,and 1-alkenyl groups. Among them, fluorine atom, trifluoromethyl groupand other groups each containing a fluorine atom are preferred. Theorganic groups include those similar to the organic groups in R^(a),R^(b), and R^(c). Preferably, R^(s) and R^(w) are bothelectron-withdrawing groups. The group R^(v) may be ahydroxyl-protecting group as in R^(d) mentioned later.

W¹ is a single bond or a linkage group. Such linkage groups include, butare not limited to, methylene group, ethylene group, and other alkylenegroups; alkenylene groups; phenylene group and other arylene groups;ester bond (—C(═O)—O—); ketone group (—C(═O)—); oxygen atom (etherbond); sulfur atom (thioether bond); and divalent groups each comprisinga plurality of these groups bonded with each other. W¹ may be a singlebond or an ester bond in many cases and is typically preferably a singlebond.

At least two of R^(a), R^(b), R^(c), R^(s), R^(v), R^(w), W¹, and carbonatoms constituting ring A¹ may be combined to form a ring, respectively.Such rings include, but are not limited to, cyclopropane, cyclobutane,cyclopentane, cyclopentene, cyclohexane, cyclohexene, cyclooctane,cyclodecane, cyclododecane ring, decalin ring, adamantane ring,norbornane ring, norbornene ring, and other non-aromatic carbocyclicrings (cycloalkane rings, cycloalkene rings, and bridged carbocyclicrings) each containing from about 3 to about 20 members, preferably fromabout 3 to about 15 members, more preferably from about 5 to about 15members, and typically from about 5 to about 8 members; and non-aromaticoxygen-atom-containing heterocyclic rings. These rings may havesubstituents such as the substituents which the hydrocarbon groups mayhave and may carry another ring (a non-aromatic ring or an aromaticring) condensed thereto.

When a carbon atom constituting ring A¹ is combined with R^(a), R^(b),R^(c), R^(s), R^(v), R^(w), or W¹, a condense ring is formed. Suchcondensed rings include the bridged rings such as adamantane ring,norbornane ring, norbornene ring, and other bridged carbocyclic rings;3-oxatricyclo[4.3.1.1^(4,8)]undecane ring,2-oxabicyclo[3.2.1^(1,5)]octane ring, 3-oxabicyclo[3.2.1^(1,5)]octanering, 2-oxabicyclo[2.2.2^(1,4)]]octane ring,6-oxatricyclo[3.2.1.1^(3,8)]nonane ring, and otheroxygen-atom-containing bridged heterocyclic rings.

The position on ring A¹ at which W¹ is combined is not specificallylimited, but is often a bridgehead position when ring A¹ forms a bridgedring.

Typical examples of the monomers each containing an electron-withdrawinggroup represented by Formula (a) are the compounds represented byFormula (a1), such as the polymerizable adamantane derivatives eachcontaining a fluorine atom represented by Formula (12), and thenorbornene derivatives each containing a fluorine atom represented byFormula (17).

In the monomers (polymerizable cyclic compounds) each containing anelectron-withdrawing group represented by Formula (b), ring A² includesnon-aromatic carbocyclic rings such as cyclopentane ring, cyclohexanering, cycloheptane ring, cyclooctane ring, cyclodecane ring, andcyclododecane ring. The repetition number n is an integer of from 2 to25, preferably an integer of from 4 to 19, and more preferably aninteger of from 4 to 14. Ring A² may have a substituent. Suchsubstituents include groups similar to the substituents which theorganic groups and the hydrocarbon groups may have.

R^(a), R^(b), R^(c), and R^(u) are the same or different and are each ahydrogen atom or an organic group. The plural R^(u)s may be the same ordifferent. The organic group includes similar groups as above.

Preferred R^(a), R^(b), R^(c), and R^(u) include hydrogen atom; methyl,ethyl, propyl, isopropyl, butyl, and other C₁-C₁₀ aliphatic hydrocarbongroups (specifically, C₁-C₄ alkyl groups); alicyclic hydrocarbon groups(specifically, C₃-C₁₅ cycloalkyl groups or cycloalkenyl groups); C₆-C₁₄aryl groups; trifluoromethyl group and other halogenated hydrocarbongroups; fluorine atom, chlorine atom, and other halogen atoms. R^(t) maybe a hydroxyl-protecting group as in R^(f) mentioned later.

The electron-withdrawing groups and organic groups in R^(w1) and R^(t)include similar groups to the electron-withdrawing groups and organicgroups in, for example, R^(s). R^(w1) is preferably anelectron-withdrawing group, of which fluorine atom, trifluoromethylgroup and other groups each containing a fluorine atom are typicallypreferred. W¹ has the same meaning as in Formula (a).

At least two of R^(a), R^(b), R^(c), R^(t), R^(u), R^(w1), W¹, andcarbon atoms constituting ring A² may be combined to form a ring,respectively. Such rings include, for example, similar rings to thoseformed by at least two of, for example, R^(a) and R^(b) in the compoundsrepresented by Formula (a).

When a carbon atom constituting ring A² is combined with R^(a), R^(b),R^(c), R^(t), R^(u), R^(w1), or W¹, a condensed ring is formed. Suchcondensed rings include the bridged rings such as adamantane ring,norbornane ring, norbornene ring, and other bridged carbocyclic rings;3-oxatricyclo[4.3.1.1^(4,8)]undecane ring,2-oxabicyclo[3.2.1^(1,5)]octane ring, 3-oxabicyclo[3.2.1^(1,5)]octanering, 2-oxabicyclo[2.2.2^(1,4)]octane ring,6-oxatricyclo[3.2.1.1^(3,8)]nonane ring, and otheroxygen-atom-containing bridged heterocyclic rings.

The position on ring A² at which W¹ is combined is not specificallylimited, but is often a bridgehead position when ring A² forms a bridgedring.

Typical examples of the monomers each containing an electron-withdrawinggroup represented by Formula (b) include the compounds represented byFormula (b1) such as the polymerizable adamantane derivatives eachcontaining a fluorine atom represented by Formula (1a), and norbornenederivatives each containing a fluorine atom. Such norbornene derivativesare compounds represented by Formula (16) in which Z is a single bondand R^(y) is a —OR^(d).

In the monomers (polymerizable cyclic compounds) each containing anelectron-withdrawing group represented by Formula (c), ring A³ includes,for example, non-aromatic oxygen-atom-containing heterocyclic rings suchas oxane ring, oxepane ring, oxocane ring, oxonane ring, oxecane ring,and other non-aromatic oxygen-atom-containing heterocyclic rings eachcontaining from about 6 to about 21 members. The repetition number n isan integer of from 2 to 25, preferably an integer of from 4 to 19, andmore preferably an integer of from 4 to 14. Ring A³ may have asubstituent. Such substituents include groups similar to thesubstituents which the organic groups and the hydrocarbon groups mayhave.

R^(a), R^(b), R^(c), and R^(u) are the same or different and are each ahydrogen atom or an organic group. The plural R^(u)s may be the same ordifferent. The organic group includes similar groups as above.

Preferred R^(a), R^(b), R^(c), and R^(u) include hydrogen atom; methyl,ethyl, propyl, isopropyl, butyl, and other C₁-C₁₀ aliphatic hydrocarbongroups (specifically, C₁-C₄ alkyl groups); alicyclic hydrocarbon groups(specifically, C₃-C₁₅ cycloalkyl groups or cycloalkenyl groups); C₆-C₁₄aryl groups; trifluoromethyl group and other halogenated hydrocarbongroups; fluorine atom, chlorine atom, and other halogen atoms.

The two R^(w2)s are both electron-withdrawing groups or one is anelectron-withdrawing group and the other is a hydrogen atom or anorganic group. Such electron-withdrawing groups and organic groups aresimilar to those mentioned above. Preferably, the two R^(w2)s are bothelectron-withdrawing groups. In this case, the two electron-withdrawinggroups as R^(w2)s may be the same or different. As theelectron-withdrawing groups, fluorine atom, trifluoromethyl group, andother groups containing a fluorine atom are preferred. W¹ has the samemeaning as in Formula (a).

At least two of R^(a), R^(b), R^(c), R^(u), R^(w2), W¹, and carbon atomsconstituting ring A³ may be combined to form a ring, respectively. Suchrings include, for example, similar rings to those formed by at leasttwo of, for example, R^(a) and R^(b) in the compounds represented byFormula (a).

When a carbon atom constituting ring A³ is combined with R^(a), R^(b),R^(c), R^(u), R^(w2), or W¹, a condensed ring is formed. Such condensedrings include, for example, 3-oxatricyclo[4.3.1.1^(4,8)]undecane ring,2-oxabicyclo[3.2.1^(1,5)]octane ring, 3-oxabicyclo[3.2.1^(1,5)]octanering, 2-oxabicyclo[2.2.2^(1,4)]]octane ring,6-oxatricyclo[3.2.1.1^(3,8)]nonane ring, and otheroxygen-atom-containing bridged heterocyclic rings.

The position on ring A³ at which W¹ is combined is not specificallylimited, but is often a bridgehead position when ring A³ forms a bridgedring.

Typical examples of the monomers each containing an electron-withdrawinggroup represented by Formula (c) include the compounds represented byFormula (c1) such as the polymerizable3-oxatricyclo[4.3.1.1^(4,8)]undecane derivatives each containing afluorine atom represented by Formula (1b), and polymerizable2-oxabicyclo[3.2.1^(1,5)]octane derivatives. The polymerizable2-oxabicyclo[3.2.1^(1,5)]octane derivatives each containing a fluorineatom are compounds represented by Formula (16) in which Z is an oxygenatom and R^(x) and R^(y) are groups each containing a fluorine atom.

In the monomers (polymerizable cyclic compounds) each having anelectron-withdrawing group represented by Formula (g), ring A⁴ issimilar to ring A¹ in Formula (a), and R^(a), R^(b), R^(c), R^(s),R^(w), R^(v), and W¹ are similar to those in Formula (a). The linkagegroup in W² includes, but is not limited to, methylene group, ethylenegroup, and other alkylene groups; alkenylene groups; phenylene group andother arylene groups; ester bond (—C(═O)—O—); ketone group (—C(═O)—);oxygen atom (ether bond); sulfur atom (thioether bond); —NH—; anddivalent groups comprising a plurality of these groups bonded with eachother. The linkage groups may each have a substituent. W² is often anester bond (—C(═O)—O—); ketone group (—C(═O)—); oxygen atom (etherbond); sulfur atom (thioether bond); —NH—; or —CH₂—O—.

At least two of R^(a), R^(b), R^(c), R^(s), R^(v), R^(w), W¹, W², andcarbon atoms constituting ring A⁴ may be combined to form a ring,respectively. Such rings include, for example, similar rings to thoseformed by at least two of R^(a), R^(b), R^(c), R^(s), R^(v), R^(w), W¹,and carbon atoms constituting ring A¹ in the compounds represented byFormula (a).

When a carbon atom constituting ring A⁴ is combined with R^(a), R^(b),R^(c), R^(s), R^(v), R^(w), W¹ or W², a condensed ring is formed. Suchcondensed rings include the bridged rings such as adamantane ring,norbornane ring, norbornene ring, and other bridged carbocyclic rings;3-oxatricyclo[4.3.1.1^(4,8)]undecane ring,2-oxabicyclo[3.2.1^(1,5)]octane ring, 3-oxabicyclo[3.2.1^(1,5)]octanering, 2-oxabicyclo[2.2.2^(1,4)]]octane ring,6-oxatricyclo[3.2.1.1^(3,8)]nonane ring, and otheroxygen-atom-containing bridged heterocyclic rings.

The position on ring A⁴ at which W¹ is combined is not specificallylimited, but is often a bridgehead position when ring A⁴ is a bridgedring. The position on ring A⁴ at which W² is combined is notspecifically limited.

Typical examples of the monomers each containing an electron-withdrawinggroup represented by Formula (g) include the compounds represented byFormulae (g1) and (g2), such as the norbornene derivatives eachcontaining a fluorine atom represented by Formula (18).

In the monomers (polymerizable cyclic compounds) each containing anelectron-withdrawing group represented by Formula (h), ring A⁵ issimilar to ring A³ in Formula (c), and R^(a), R^(b), R^(c), R^(u),R^(w2), W¹, and n are similar to those in Formula (c). G¹ is a linkagegroup comprising a hetero atom, and G² is a single bond or a linkagegroup comprising a hetero atom. When G¹ is an oxygen atom, G² is alinkage group comprising a hetero atom.

Such linkage groups each comprising a hetero atom may be divalent groupseach comprising at least one (for example, one to three) hetero atom ina principle chain. Such groups include, for example, oxygen atom (etherbond), sulfur atom (thioether bond), —S(═O)—O—, —S(═O)₂—O—, —NH—,silicon atom (—Si—), and —OP(═O) —O—. Among them, oxygen atom (etherbond), sulfur atom (thioether bond), —S(═O)—O—, and —S(═O)₂—O— arepreferred.

At least two of R^(a), R^(b), R^(c), R^(u), R^(w2), W¹, and carbon atomsconstituting ring A⁵ may be combined to form a ring, respectively. Suchrings include, for example, similar rings to those formed by at leasttwo of R^(a), R^(b), R^(c), R^(s), R^(v), R^(w), W¹, and carbon atomsconstituting ring A¹ in the compounds represented by Formula (a).

When a carbon atom constituting ring A⁵ is combined with R^(a), R^(b),R^(c), R^(u), R^(w2) or W¹, a condensed ring is formed. Such condensedrings include the bridged rings such as adamantane ring, norbornanering, norbornene ring, and other bridged carbocyclic rings;3-thiatricyclo[4.3.1.1^(4,8)]undecane ring,2-thiabicyclo[3.2.1^(1,5)]octane ring, 3-thiabicyclo[3.2.1^(1,5)]octanering, 2-thiabicyclo[2.2.2^(1,4)]]octane ring,6-thiatricyclo[3.2.1.1^(3,8)]nonane ring, and othersulfur-atom-containing bridged heterocyclic rings.

The position on ring A⁵ at which W¹ is combined is not specificallylimited, but is often a bridgehead position when ring A⁵ is a bridgedring.

Typical examples of the monomers each containing an electron-withdrawinggroup represented by Formula (h) include the compounds represented byFormula (h), such as the norbornene derivatives each containing anelectron-withdrawing group represented by Formula (19) or (20).

In the monomers (polymerizable cyclic compounds) each containing anelectron-withdrawing group represented by Formula (i), A⁶ is preferablya non-aromatic heterocyclic ring such as dioxolene ring and dithiolenering. R^(a), R^(c), and R^(u) are similar to those in Formula (c). Theorganic group and electron-withdrawing group in R^(w3) are similar tothose in R^(w2) in Formula (c). The repetition numbers m1 and m2 areeach an integer of from 0 to 2. The linkage groups comprising a heteroatom in G³ and G⁴ include similar groups to those in G¹. Among them,oxygen atom (ether bond), sulfur atom (thioether bond), —S(═O)—O—, and—S(═O)₂—O— are preferred.

At least two of R^(a), R^(c), R^(u), R^(w3), and carbon atomsconstituting ring A⁶ may be combined to form a ring, respectively. Suchrings include, for example, similar rings to those formed by at leasttwo of R^(a), R^(b), R^(c), R^(s), R^(v), R^(w), W¹, and carbon atomsconstituting ring A¹ in Formula (a).

Typical examples of the monomers each containing an electron-withdrawinggroup represented by Formula (i) include the compounds represented byFormula (i1), such as the heterocyclic compounds each containing anelectron-withdrawing group represented by Formula (21).

In the monomers (polymerizable cyclic compounds) each containing anelectron-withdrawing group represented by Formula (j), A⁷ is preferablya non-aromatic heterocyclic ring such as oxolene ring and thiolene ring.R^(a), R^(c), and R^(u) are similar to those in Formula (c). The organicgroup and electron-withdrawing group in R^(w4) are similar to those inR^(w2) in Formula (c). The repetition numbers m1 and m2 are each aninteger of from 0 to 2. The linkage group comprising a hetero atom in G⁵includes similar groups to those in G¹. Among them, oxygen atom (etherbond), sulfur atom (thioether bond), —S(═O)—O—, and —S(═O)₂—O— arepreferred.

At least two of R^(a), R^(c), R^(u), R^(w4), and carbon atomsconstituting ring A⁷ may be combined to form a ring, respectively. Suchrings include, for example, similar rings to those formed by at leasttwo of R^(a), R^(b), R^(c), R^(s), R^(v), R^(w), W¹, and carbon atomsconstituting ring A¹ in Formula (a).

Typical examples of the monomers each containing an electron-withdrawinggroup represented by Formula (j) include the compounds represented byFormula (j1), such as the heterocyclic compounds containing anelectron-withdrawing group represented by Formula (22).

In the monomers containing an electron-withdrawing group of the presentinvention, the electron-withdrawing groups in R^(s), R^(v), R^(w),R^(t), R^(w1), R^(w2), R^(w3) and R^(w4) are specifically preferablygroups each containing a fluorine atom. Ring A¹, ring A², ring A³, ringA⁴ or ring A⁵ is preferably a monocyclic ring or bridged ring containingat least a 5- to 7-membered carbocyclic ring or oxygen-containingheterocyclic ring. Preferred monomers containing an electron-withdrawinggroup have a bridged cyclic skeleton including ring A¹, ring A², ringA³, ring A⁴ or ring A⁵ and containing from 7 to 15 carbon atoms. Ring A⁶and ring A⁷ are preferably 5- or 6-membered oxygen-containingheterocyclic rings or 5- or 6-membered sulfur-containing heterocyclicrings.

[Compounds Represented by Formula (b1) and Production Thereof]

The compounds represented by Formula (b1) correspond to compoundsrepresented by Formula (b) in which R^(w1) is a group containing afluorine atom; and R^(t) is a hydrogen atom or a hydroxyl-protectinggroup.

In Formula (b1), the group containing a fluorine atom in R^(x) includes,for example, fluorine atom and trifluoromethyl group. Thehydroxyl-protecting group in R^(d) includes, but is not limited to,alkyl groups (e.g., methyl, t-butyl, and other C₁-C₄ alkyl groups),alkenyl groups (e.g., allyl group), cycloalkyl groups (e.g., cyclohexylgroup), aryl groups (e.g., 2,4-dinitrophenyl group), aralkyl groups(e.g., benzyl, 2,6-dichlorobenzyl, 3-bromobenzyl, 2-nitrobenzyl, andtriphenylmethyl groups); substituted methyl groups (e.g., methoxymethyl,methylthiomethyl, benzyloxymethyl, t-butoxymethyl,2-methoxyethoxymethyl, 2,2,2-trichloroethoxymethyl,bis(2-chloroethoxy)methyl, and 2-(trimethylsilyl)ethoxymethyl groups),substituted ethyl groups (e.g., 1-ethoxyethyl, 1-methyl-1-methoxyethyl,1-isopropoxyethyl, and 2,2,2-trichloroethyl groups), tetrahydropyranylgroup, tetrahydrofuranyl group, 1-hydroxyalkyl groups (e.g.,1-hydroxyethyl, 1-hydroxyhexyl, 1-hydroxydecyl, and 1-hydroxyhexadecylgroups), and other groups that can form an acetal or hemiacetal groupwith a hydroxyl group; acyl groups (e.g., formyl, acetyl, propionyl,butyryl, isobutyryl, valeryl, pivaloyl, and other C₁-C₆ aliphatic acylgroups; acetoacetyl group; benzoyl, naphthoyl, and other aromatic acylgroups), alkoxycarbonyl groups (e.g., methoxycarbonyl, ethoxycarbonyl,t-butoxycarbonyl, and other C₁-C₄ alkoxy-carbonyl groups),aralkyloxycarbonyl groups (e.g., benzyloxycarbonyl group andp-methoxybenzyloxycarbonyl group), substituted or unsubstitutedcarbamoyl groups (e.g., carbamoyl, methylcarbamoyl, and phenylcarbamoylgroups), dialkylphosphinothioyl groups, diarylphosphinothioyl groups,substituted silyl groups (e.g., trimethylsilyl, t-butyldimethylsilyl,tribenzylsilyl, and triphenylsilyl groups), and groups each containing afluorine atom (e.g., trifluoromethyl group). Preferredhydroxyl-protecting groups include C₁-C₄ alkyl groups; substitutedmethyl groups, substituted ethyl groups, 1-hydroxyalkyl groups, andother groups that can form an acetal or hemiacetal group with a hydroxylgroup; acyl groups, C₁-C₄ alkoxy-carbonyl groups, substituted orunsubstituted carbamoyl groups, and substituted silyl groups.

Each of the monomers containing a fluorine atom and having an ethylenicdouble bond represented by Formula (b1) can be produced by allowing thecyclic ketone having an ethylenic double bond represented by Formula (d)to react with a fluorine reagent or subjecting the cyclic ketone havingan ethylenic double bond represented by Formula (d) to a reaction with afluorine reagent and to a subsequent reaction for introducing aprotecting group.

The symbols in Formula (d) have the same meanings as above. The fluorinereagent is not specifically limited as long as it is a reagent that canintroduce a group containing a fluorine atom into a carbonyl carbonatom. Among such fluorine reagents, trimethyl(trifluoromethyl)silane[TMS-CF₃], trifluoromethyl bromide [CF₃Br], and othertrifluoromethylating agents and fluorinating agents are preferred.

A reaction can be performed under a conventional condition withreference to the type of the fluorine reagent. For example, when TMS-CF₃is used, the reaction is preformed in an appropriate solvent, such astetrahydrofuran, and preferably in the presence of a catalyst such as aquaternary ammonium salt. The quaternary ammonium salt includes, forexample, tetrabutylammonium fluoride. A reaction temperature is fromabout −10° C. to about 50° C. The amount of the trifluoromethylatingagent is, for example, from about 0.9 to about 1.5 moles per mole of thecompound represented by Formula (d). After the completion of thereaction, the resulting reaction mixture is quenched by adding, forexample, diluted hydrochloric acid, and the target compound can beseparated and purified by a separation means such as extraction,distillation, crystallization, recrystallization, and columnchromatography. The reagent CF₃Br is generally used in combination withZn/PdCl₂(PPh₃), Zn/Cp₂TiCl₂, Zn/pyridine, or Zn/tetrabutylammonoiumfluoride, for example.

When the trifluoromethylating agent is used as the fluorine reagent,compounds represented by Formula (b1) where R^(x) is a trifluoromethylgroup are obtained under normal conditions.

Compounds represented by Formula (b1) where R^(d) is ahydroxyl-protecting group can be produced by subjecting compounds whereR^(d) is a hydrogen atom, which are obtained according to the aboveprocedure, to a reaction for introducing a protecting group according tothe type of the protecting group. Such reactions for introducing aprotecting group include conventional reactions generally employed inthe field of organic synthesis.

[Compounds Represented by Formula (c1) and Production Thereof]

The compounds represented by Formula (c1) correspond to compoundsrepresented by Formula (c) in which the two R^(w2)s are groupscontaining a fluorine atom. In Formula (c1), the groups containing afluorine atom in R^(x) and R^(y1) include, for example, fluorine atomand trifluoromethyl group.

Each of the monomers containing a fluorine atom and having an ethylenicdouble bond represented by Formula (c1) can be produced by allowing thecyclic thioester having an ethylenic double bond represented by Formula(e) to react with a fluorine reagent. The symbols in Formula (e) havethe same meanings as above.

Such fluorine reagents are not specifically limited as long as they arereagents that can convert a thiocarbonyl group into a methylene grouphaving a group containing a fluorine atom. Among them,diethylaminosulfur trifluoride (DAST) tetrabutylammonium fluoride-(HF)₂,TBA⁺H₂F₃ ⁻/N-bromosuccinimide, and other fluorinating agents (reagentsfor introducing a fluorine atom) and trifluoromethylating agents arepreferred. The term “TBA⁺” means a tetrabutylammonium ion.

A reaction can be performed under a conventional condition withreference to the type of the fluorine reagent. For example, when afluorinating agent is used as the fluorine reagent, the reaction isperformed in an appropriate solvent such as methylene chloride at atemperature of from about −70° C. to about 50° C. The amount of thefluorinating agent is from about 0.9 to about 5 moles per mole of thecompound represented by Formula (e) After the completion of thereaction, the target compound can be separated and purified by aseparation means such as extraction, distillation, crystallization,recrystallization, or column chromatography. When the fluorinating agentis used, compounds represented by Formula (c1) in which R^(x) and R^(y1)are fluorine atoms are obtained under normal conditions.

[Compounds Represented by Formula (e)]

Each of the monomers having a cyclic thioester skeleton represented byFormula (e) can be produced, for example, by allowing a correspondingcompound having a cyclic ester (lactone) skeleton to react with asulfurizing agent. Such sulfurizing agents are not specifically limitedas long as they can convert a carbonyl group into a thiocarbonyl group.Among them, 2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane2,4-disulfide (Lawesson reagent) is typically preferred. A reaction isperformed in an appropriate solvent such as toluene at a temperature offrom about 50° C. to about 200° C. The amount of the sulfurizing agentis from about 0.9 to about 2 moles per mole of the lactone. After thecompletion of the reaction, the polymerizable cyclic compoundrepresented by Formula (e) can be separated and purified by a separationmeans such as extraction, distillation, crystallization,recrystallization, or column chromatography.

Typical examples of the compounds represented by Formula (e) includecompounds represented by Formula (3a) mentioned later.

[Polymerizable Bridged Cyclic Compounds (1) Containing a Fluorine Atom]

In the polymerizable bridged cyclic compounds each containing a fluorineatom represented by Formula (1), R^(a), R^(b), and R^(c) are the same ordifferent and are each a hydrogen atom or an organic group. Such organicgroups are similar to those mentioned above.

Preferred R^(a), R^(b), and R^(c) include hydrogen atom; methyl, ethyl,propyl, isopropyl, butyl, and other C₁-C₁₀ aliphatic hydrocarbon groups(specifically, C₁-C₄ alkyl groups); alicyclic hydrocarbon groups(specifically, C₃-C₁₅ cycloalkyl groups or cycloalkenyl groups); C₆-C₁₄aryl groups; trifluoromethyl group and other halogenated hydrocarbongroups; fluorine atom, chlorine atom, and other halogen atoms.Alternatively, R^(a) and R^(b) are preferably combined to form anon-aromatic carbocyclic ring containing from about 3 to about 15members (typically from about 5 to about 10 members) with the adjacentcarbon atom. Typically preferred R^(a), R^(b), and R^(c) are hydrogenatoms or methyl groups.

The ethenyl group having R^(a), R^(b), and R^(c) in Formula (1) may becombined with any of carbon atoms constituting a bridged ring but isoften combined with a carbon atom at a bridgehead position. The bondingposition of the ethenyl group or its precursor (e.g., a hydroxyalkylgroup in Formula (4) or an acyl group in Formula (6)) in startingmaterials and intermediates mentioned later is similar to that inFormula (1).

In the polymerizable bridged cyclic compounds containing a fluorine atomrepresented by Formula (1), R^(x) is a trifluoromethyl group and R^(y)is a —OR^(d) group, where R^(d) is hydrogen atom or ahydroxyl-protecting group, when Z is a single bond. R^(x) and R^(y) arefluorine atoms when Z is an oxygen atom. Specifically, the compoundsrepresented by Formula (1) include the trifluoromethyladamantanederivatives represented by Formula (1a) and2,2-difluoro-3-oxatricyclo[4.3.1.1^(4,8)]undecane derivativesrepresented by Formula (1b).

The hydroxyl-protecting group in R^(d) is similar to that mentionedabove.

Carbon atoms constituting the ring in Formula (1) (carbon atoms atbridgehead positions and/or carbon atoms at non-bridgehead positions)may each have a substituent. Such substituents include, but are notlimited to, methyl group, ethyl group, isopropyl group, and other C₁-C₄alkyl groups, hydroxyl group which may be protected by a protectinggroup, hydroxyalkyl groups which may be protected by a protecting group,carboxyl group which may be protected by a protecting group, amino groupwhich may be protected by a protecting group, halogen atoms, oxo group,nitro group, and halogenated alkyl groups such as trifluoromethyl group.As the protecting groups, conventional protecting groups in the field oforganic synthesis can be used. When starting materials or intermediatesused in production of the polymerizable bridged cyclic compoundscontaining a fluorine atom of the present invention are compounds eachhaving a ring, carbon atoms constituting the ring may each have asubstituent. Such substituents include the aforementioned substituents.

Typical examples of the polymerizable bridged cyclic compounds eachcontaining a fluorine atom represented by Formula (1) include2-trifluoromethyl-2-hydroxy-5-vinyladamantane,2-trifluoromethyl-2-methoxy-5-vinyladamantane,2-trifluoromethyl-2-hydroxy-5-(1-propenyl)adamantane,2-trifluoromethyl-2-hydroxy-5-(1-methylethenyl)adamantane, and otheradamantane derivatives each having a trifluoromethyl group and ahydroxyl group which may be protected by a protecting group at the2-position and an ethylenic double bond at the 5-position;2,2-difluoro-6-vinyl-3-oxatricyclo[4.3.1.1^(4,8)]undecane,2,2-difluoro-6-(1-propenyl)-3-oxatricyclo[4.3.1.1^(4,8)]undecane,2,2-difluoro-6-(1-methylethenyl)-3-oxatricyclo[4.3.1.1^(4,8)]undecane,and other 3-oxatricyclo[4.3.1.1.^(4,8)]undecane derivatives each havingtwo fluorine atoms at the 2-position and an ethylenic double bond at the6-position;2,2-bis(trifluoromethyl)-6-vinyl-3-oxatricyclo[4.3.1.1^(4,8)]undecane,2,2-bis(trifluoromethyl)-6-(1-propenyl)-3-oxatricyclo[4.3.1.1^(4,8)]undecane,2,2-bis(trifluoromethyl)-6-(1-methylethenyl)-3-oxatricyclo[4.3.1.1^(4,8)]undecane,and other 3-oxatricyclo[4.3.1.1^(4,8)]undecane derivatives each havingtwo trifluoromethyl groups at the 2-position and an ethylenic doublebond at the 6-position.

The compounds represented by Formula (1) each have a polymerizableethylenic double bond, contain a bridged cyclic skeleton and a fluorineatom that impart various functions to the compounds and are thereforevery useful as, for example, monomers for functional polymers.

[Production of Polymerizable Bridged Cyclic Compounds (1) Containing aFluorine Atom]

The compounds represented by Formula (1) include the compoundsrepresented by Formula (1a) and the compounds represented by Formula(1b).

Of the adamantane derivatives each containing a fluorine atom and havingan ethylenic double bond represented by Formula (1a), a compound whereR^(d) is a hydrogen atom can be obtained, for example, by allowing theadamantanone derivative having an ethylenic double bond represented byFormula (2) to react with a fluorine reagent such as atrifluoromethylating agent.

R^(a), R^(b), and R^(c) in Formula (2) have the same meanings as above.The fluorine reagent is not specifically limited as long as it is areagent that can introduce a group containing a fluorine atom into acarbonyl carbon atom. Among such fluorine reagents,trimethyl(trifluoromethyl)silane [TMS-CF₃] and othertrifluoromethylating agents are preferred.

A reaction can be performed in the same manner as in the production ofthe compounds represented by Formula (b1). When the trifluoromethylatingagent is used as the fluorine reagent, compounds represented by Formula(1a) in which R^(x) is a trifluoromethyl group can be obtained.

Adamantane derivatives each containing a fluorine atom and having anethylenic double bond represented by Formula (1a) where R^(d) is ahydroxyl-protecting group can be produced by subjecting compounds whereR^(d) is a hydrogen atom, which are obtained according to the aboveprocedure, to a reaction for introducing a protecting group according tothe type of the protecting group. Such reactions for introducing aprotecting group include conventional reactions generally employed inthe field of organic synthesis.

Each of the 3-oxatricyclo[4.3.1.1^(4,8)]undecane derivatives containinga fluorine atom and having an ethylenic double bond represented byFormula (1b) can be produced, for example, by allowing the3-oxatricyclo[4.3.1.1^(4,8)]undecane-2-thione derivative having anethylenic double bond represented by Formula (3a) to react with afluorine reagent.

R^(a), R^(b), and R^(c) in Formula (3a) are similar to those mentionedabove. The fluorine reagent is not specifically limited as long as it isa reagent that can convert a thiocarbonyl group into a methylene grouphaving a group containing a fluorine atom. Among such fluorine reagents,diethylaminosulfur trifluoride (DAST) and other fluorinating agents(reagents for introducing a fluorine atom) are preferred.

A reaction can be performed in the same manner as in the production ofthe compounds represented by Formula (c1). When the fluorinating agentis used as the fluorine reagent, compounds represented by Formula (1b)in which R^(x) and R^(y) are fluorine atoms(2,2-difluoro-3-oxatricyclo[4.3.1.1^(4,8)]undecane derivatives) areobtained under normal conditions.

[Production of Compounds Represented by Formula (3a)]

Each of the 3-oxatricyclo[4.3.1.1^(4,8)]undecane-2-thione derivativeshaving an ethylenic double bond represented by Formula (3a) can beobtained, for example, by allowing the3-oxatricyclo[4.3.1.1^(4,8)]undecan-2-one derivative represented byFormula (3b) to react with a sulfurizing agent.

R^(a), R^(b), and R^(c) in Formula (3b) are similar to those mentionedabove. The sulfurizing agent is not specifically limited as long as itis a reagent that can convert a carbonyl group into a thiocarbonylgroup. Among such sulfurizing agents,2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane 2,4-disulfide(Lawesson reagent) is typically preferred.

A reaction is performed in an appropriate solvent such as toluene at atemperature of from about 50° C. to about 200° C. The amount of thesulfurizing agent is from about 0.9 to about 2 moles per mole of the3-oxatricyclo[4.3.1.1^(4,8)]undecan-2-one derivative represented byFormula (3b). After the completion of the reaction, the target compoundcan be separated and purified by a separation means such as extraction,distillation, crystallization, recrystallization, or columnchromatography.

Typical examples of the compounds represented by Formula (3a) thusobtained include 6-vinyl-3-oxatricyclo[4.3.1.1^(4,8)]undecane-2-thione,6-(1-propenyl)-3-oxatricyclo[4.3.1.1^(4,8)]undecane-2-thione,6-(1-methylethenyl)-3-oxatricyclo[4.3.1.1^(4,8)]undecane-2-thione, andother 3-oxatricyclo[4.3.1.1^(4,8)]undecane-2-thione derivatives eachhaving an ethylenic double bond at the 6-position.

[Production of Compounds Represented by Formula (5)]

Each of the bridged cyclic compounds having an ethylenic double bondrepresented by Formula (5) (i.e., the compounds represented by Formula(2) and the compounds represented by Formula (3b)) can be obtained, forexample, by subjecting the bridged cyclic compound containing ahydroxyalkyl group represented by Formula (4) to a dehydration reaction.

R^(a), R^(b), and R^(c) in Formula (4) are similar to those mentionedabove. Z is a single bond or an oxygen atom. When Z is a single bond,the bridged ring in the formula is an adamantane ring. When Z is anoxygen atom, the bridged ring in the formula is an3-oxatricyclo[4.3.1.1^(4,8)]undecane ring.

The dehydration reaction is performed in an appropriate solvent such astoluene, where necessary in the presence of sulfuric acid or anotheracid or a dehydrating agent, at a temperature of from about 0° C. toabout 150° C. The dehydration reaction may be performed while distillingoff water which is by-produced as a result of azeotropy. After thecompletion of the reaction, the target compound can be separated andpurified by a separation means such as extraction, distillation,crystallization, recrystallization, or column chromatography.

Typical examples of the compounds represented by Formula (5) thusobtained include 1-vinyladamantan-4-one, 1-(1-propenyl)adamantan-4-one,1-(1-methylethenyl)adamantan-4-one, and other adamantan-4-onederivatives each having an ethylenic double bond at the 1-position;6-vinyl-3-oxatricyclo[4.3.1.1^(4,8)]undecan-2-one,6-(1-propenyl)-3-oxatricyclo[4.3.1.1^(4,8)]undecan-2-one,6-(1-methylethenyl)-3-oxatricyclo[4.3.1.1^(4,8)]undecan-2-one, and other3-oxatricyclo[4.3.1.1^(4,8)]undecan-2-one derivatives each having anethylenic double bond at the 6-position.

[Production of Compounds Represented by Formula (4)]

Each of the bridged cyclic compounds each containing a hydroxyalkylgroup represented by Formula (4) can be obtained, for example, bysubjecting the bridged cyclic compound containing an acyl grouprepresented by Formula (6) to reduction or to a reaction with theorganometallic compound represented by Formula (9). When the bridgedcyclic compound containing an acyl group represented by Formula (6) isreduced, compounds represented by Formula (4) in which R^(c) is ahydrogen atom are obtained. When the bridged cyclic compound containingan acyl group represented by Formula (6) is subjected to a reaction withthe organometallic compound represented by Formula (9), compoundsrepresented by Formula (4) in which R^(c) is R^(c1) (an organic group)are obtained. R^(a), R^(b), and Z in Formula (6) are similar to thosementioned above.

The bridged cyclic compound containing an acyl group represented byFormula (6) can be reduced, for example, by reduction using a metalhydride complex compound such as lithium aluminium hydride or sodiumborohydride; reduction using a borane; or catalytic reduction usinghydrogen and a Rh catalyst. Reduction is performed in a solvent at atemperature of from about −100° C. to about 150° C. Such solvents areselected, depending on the type of the reduction process, from diethylether, tetrahydrofuran, and other ethers; hexane and other aliphatichydrocarbons; cyclohexane and other alicyclic hydrocarbons; toluene andother aromatic hydrocarbons; methanol, ethanol, and other alcohols;acetic acid and other carboxylic acids; methylene chloride and otherhalogenated hydrocarbons. After the completion of the reaction, theresulting reaction mixture is quenched for example with water accordingto necessity, and the target compound can be separated and purified by aseparation means such as extraction, distillation, crystallization,recrystallization, or column chromatography.

In the organometallic compounds represented by Formula (9), R^(c1) is anorganic group; and M is a metallic atom which may have a ligand, or thegroup represented by Formula (10). The organic group in R^(c1) issimilar to that in R^(c).

The metallic atom in M includes, but is not limited to, lithium andother alkali metal atoms, cerium, titanium, copper, and other transitionmetal atoms. These metallic atoms may each have a ligand. The term“ligand” as used herein also means and includes atoms or atomic groupscorresponding to cations in ate complexes. Such ligands include, forexample, chlorine atom and other halogen atoms, isopropoxy group andother alkoxy groups, diethylamino group and other dialkyl amino groups,cyano group, alkyl groups, lithium atom and other alkali metal atoms (ascations in ate complexes). The halogen atom represented by X¹ in Formula(10) includes, for example, chlorine, bromine, and iodine atoms. Typicalexamples of the organometallic compounds represented by Formula (9)include dimethyldiisopropoxytitanium and other organic titaniumcompounds (including ate complexes of organic titanium), organicmagnesium compounds (e.g., Grignard reagents), and organic lithiumcompounds.

The amount of the organometallic compound represented by Formula (9) is,for example, from about 0.9 to about 1.5 moles per mole of the bridgedcyclic compound containing an acyl group represented by Formula (6). Areaction is usually performed in an organic solvent. Such organicsolvents include, but are not limited to, the aforementioned ethers andaliphatic hydrocarbons. A reaction temperature can appropriately beselected within the range of from about −100° C. to about 150° C.depending on the type of the reaction components and other factors.After the completion of the reaction, the resulting reaction mixture isusually quenched with an aqueous solution containing an acid (e.g.,hydrochloric acid) or a salt (e.g., ammonium chloride), and thealkalinity or acidity of the resulting mixture is adjusted according tonecessity. Thereafter, the target compound can be separated and purifiedby a separation means such as filtration, concentration, extraction,distillation, crystallization, recrystallization, or columnchromatography.

Typical examples of the compounds represented by Formula (4) thusobtained include 1-(1-hydroxyethyl)adamantan-4-one,1-(1-hydroxypropyl)adamantan-4-one,1-(1-hydroxy-1-methylethyl)adamantan-4-one, and other adamantan-4-onederivatives each having a 1-hydroxyalkyl group at the 1-position;6-(1-hydroxyethyl)3-oxatricyclo[4.3.1.1^(4,8)]undecan-2-one,6-(1-hydroxypropyl)3-oxatricyclo[4.3.1.1^(4,8)]undecan-2-one,6-(1-hydroxy-1-methylethyl)3-oxatricyclo[4.3.1.1^(4,8)]undecan-2-one,and other 3-oxatricyclo[4.3.1.1^(4,8)]undecan-2-one derivatives eachhaving a 1-hydroxyalkyl group at the 6-position.

[Production of Compounds Represented by Formula (6)]

Each of the bridged cyclic compounds each containing an acyl grouprepresented by Formula (6) can be obtained, for example, by allowing thebridged cyclic compound represented by Formula (7) to react with anacylating agent comprising (A) the 1,2-dicarbonyl compound or itshydroxy reductant represented by Formula (8), (B) oxygen, and (C) atleast one compound selected from (c1) metallic compounds and (c2)N-hydroxy or N-oxo cyclic imide compounds.

Z in Formula (7) and R^(a) and R^(b) in Formula (8) are similar to thosementioned above. R in Formula (8) is a hydrogen atom or an organicgroup. The organic group in R is similar to the organic groups in R^(a),R^(b), and R^(c). Z¹ and Z² are the same or different and are each anoxygen atom or a hydroxyl group, and the bond between a carbon atom andZ¹ or Z² is a single bond or a double bond.

The bridged cyclic compound represented by Formula (7) can be obtainedaccording to a conventional procedure or a similar procedure thereto.

In the components (A), typical examples of the 1,2-dicarbonyl compoundsinclude biacetyl(2,3-butanedione), 2,3-pentanedione, 3,4-hexanedione,acetylbenzoyl, and other α-diketones. Typical examples of the hydroxyreductants of the 1,2-dicarbonyl compounds include acetoin and otherα-keto-alcohols; 2,3-butanediol, 2,3-pentanediol, and other vicinaldiols.

Oxygen (B) may be either molecular oxygen or active oxygen (oxygenradical). The molecular oxygen includes, but is not limited to, pureoxygen, and oxygen diluted with an inert gas such as nitrogen, helium,argon or carbon dioxide, as well as air. As oxygen (B), molecular oxygenis frequently used.

Metallic elements to constitute the metallic compounds (C1) are notspecifically limited, and can be any metallic element of Groups 1 to 15of the Periodic Table of Elements. The term “metallic element” as usedherein also means and includes boron, B. Examples of the metallicelements include, of the Periodic Table of Elements, Group 1 elements(e.g., Li, Na, and K), Group 2 elements (e.g., Mg, Ca, Sr, and Ba),Groups 3 elements (e.g., Sc, lanthanoid elements, and actinoidelements), Group 4 elements (e.g., Ti, Zr, and Hf), Group 5 elements(e.g., V), Group 6 elements (e.g., Cr, Mo, and W), Group 7 elements(e.g., Mn), Group 8 elements (e.g., Fe and Ru), Group 9 elements (e.g.,Co and Rh), Group 10 elements (e.g., Ni, Pd, and Pt), Group 11 elements(e.g., Cu), Group 12 elements (e.g., Zn), Groups 13 elements (e.g., B,Al, and In), Group 14 elements (e.g., Sn and Pb), and Group 15 elements(e.g., Sb and Bi). Preferred metallic elements include transition metalelements (elements of Groups 3 to 12 of the Periodic Table of Elements).Among them, elements of the Groups 5 to 11 of the Periodic Table ofElements are preferred, of which Group 5 elements and Group 9 elementsare typically preferred. Especially, Co and V can advantageously beused. The valence of the metallic element is not specifically limitedand may range from about 0 to about 6.

The metallic compounds (C1) include, but are not limited to, elementarysubstances, hydroxides, oxides (including complex oxides), halides(fluorides, chlorides, bromides, and iodides), salts of oxoacids (e.g.,nitrates, sulfates, phosphates, borates, and carbonates), oxoacids,isopoly acids, heteropoly acids, and other inorganic compounds of theaforementioned metallic elements; salts of organic acids (e.g.,acetates, propionates, prussiates, naphthenates, and stearates),complexes, and other organic compounds of the metallic elements. Ligandsconstituting the complexes include OH (hydroxo), alkoxy (e.g., methoxy,ethoxy, propoxy, and butoxy), acyl (e.g., acetyl and propionyl),alkoxycarbonyl (e.g., methoxycarbonyl and ethoxycarbonyl),acetylacetonato, cyclopentadienyl group, halogen atoms (e.g., chlorineand bromine), CO, CN, oxygen atom, H₂O (aquo),phosphine(triphenylphosphine and other triarylphosphines) and otherphosphorus compounds, NH₃ (ammine), NO, NO₂ (nitro), NO₃ (nitrate),ethylenediamine, diethylenetriamine, pyridine, phenanthroline, and othernitrogen-containing compounds.

Examples of the metallic compounds (C1) include, taking cobalt compoundsas an example, cobalt hydroxide, cobalt oxide, cobalt chloride, cobaltbromide, cobalt nitrate, cobalt sulfate, cobalt phosphate, and otherinorganic compounds; cobalt acetate, cobalt naphthenate, cobaltstearate, and other salts of organic acids; acetylacetonatocobalt, andother complexes, and other divalent or trivalent cobalt compounds.Example of the vanadium compounds include vanadium hydroxide, vanadiumoxide, vanadium chloride, vanadyl chloride, vanadium sulfate, vanadylsulfate, sodium vanadate, and other inorganic compounds;acetylacetonatovanadium, vanadyl acetylacetonato, and other complexes,and other vanadium compounds having a valence of 2 to 5. Examples of thecompounds of the other metallic elements include compounds correspondingto the above-mentioned cobalt or vanadium compounds. Each of themetallic compounds (C1) can be used alone or in combination.

The ratio of the metallic compound (C1) to the 1,2-dicarbonyl compoundor its hydroxy reductant (A) is, for example, such that the former(C1)/the latter (A) (by mole) is from about 0 to about 0.5, andpreferably from about 0.001 to about 0.2.

The N-hydroxy or N-oxocyclicimide compounds (c2) include imide compoundsrepresented by following Formula (11):

wherein R¹ and R² are the same or different and are each a hydrogenatom, a halogen atom, an alkyl group, an aryl group, a cycloalkyl group,a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonylgroup, or an acyl group, where R¹ and R² may be combined to form adouble bond or an aromatic or non-aromatic ring; X is an oxygen atom ora hydroxyl group; and one or two of N-substituted cyclic imido groupindicated in Formula (11) may further be formed on R¹, R², or on thedouble bond or aromatic or non-aromatic ring formed by R¹ and R².

Of the substituents R¹ and R² in the imide compounds represented byFormula (11), the halogen atom includes iodine, bromine, chlorine andfluorine. The alkyl group includes, but is not limited to, methyl,ethyl, propyl, hexyl, decyl, and other straight- or branched-chain alkylgroups each containing from about 1 to about 10 carbon atoms. The arylgroup includes, for example, phenyl and naphthyl groups. The cycloalkylgroup include, for example, cyclopentyl and cyclohexyl groups. Thealkoxy group includes, for example, methoxy, ethoxy, isopropoxy, andother alkoxy groups each containing from about 1 to about 10 carbonatoms. The alkoxycarbonyl group includes, for example, methoxycarbonyl,ethoxycarbonyl, isopropoxycarbonyl, and other alkoxycarbonyl groups eachcontaining from about 1 to about 10 carbon atoms in the alkoxy moiety.The acyl group includes, for example, formyl, acetyl, propionyl,butyryl, and other acyl groups each containing from about 1 to about 6carbon atoms.

The substituents R¹ and R² may be identical to or different from eachother. The substituents R¹ and R² in Formula (11) may be combined toform a double bond or an aromatic or non-aromatic ring. The preferredaromatic or non-aromatic ring has from about 5 to about 12 members, andspecifically from about 6 to about 10 members. The ring may be aheterocyclic ring or condensed heterocyclic ring, but it is often ahydrocarbon ring. Such rings include, for example, non-aromaticalicyclic rings (e.g., cyclohexane ring and other cycloalkane ringswhich may have a substituent, cyclohexene ring and other cycloalkenerings which may have a substituent), non-aromatic bridged rings (e.g.,5-norbornene ring and other bridged hydrocarbon rings which may have asubstituent), benzene ring, naphthalene ring, and other aromatic rings(including condensed rings) which may have a substituent. The ring iscomposed of an aromatic ring in many cases. The ring may have asubstituent. Such substituents include, but are not limited to, alkylgroups, haloalkyl groups, hydroxyl group, alkoxy groups, carboxyl group,alkoxycarbonyl groups, acyl groups, nitro group, cyano group, aminogroup, and halogen atoms.

In Formula (11), X is an oxygen atom or a hydroxyl group, and the bondbetween the nitrogen atom N and X is a single bond or a double bond.

One or two of the N-substituted cyclic imido group indicated in Formula(11) may be further formed on R¹, R², or on the double bond or aromaticor non-aromatic ring formed by R¹ and R².

Preferred imide compounds include, for example, N-hydroxysuccinimide,N-hydroxymaleimide, N-hydroxyhexahydrophthalimide,N,N′-dihydroxycyclohexanetetracarboximide, N-hydroxyphthalimide,N-hydroxytetrabromophthalimide, N-hydroxytetrachlorophthalimide,N-hydroxychlorendimide, N-hydroxyhimimide, N-hydroxytrimellitimide,N,N′-dihydroxypyromellitimide, andN,N′-dihydroxynaphthalenetetracarboximide.

The imide compounds can be prepared by a conventional imidation process(a process for the formation of an imide), such as a process thatcomprises the steps of allowing a corresponding acid anhydride to reactwith hydroxylamine NH₂OH for ring-opening of an acid anhydride group,and closing the ring to form an imide. Typically preferred imidecompounds include N-hydroxyimide compounds derived from alicyclicpolycarboxylic anhydrides or aromatic polycarboxylic anhydrides, ofwhich N-hydroxyimide compounds derived from aromatic polycarboxylicanhydrides, for example, N-hydroxyphthalimide are specificallypreferred. Each of these N-hydroxy or N-oxo cyclic imide compounds (c2)can be used alone or in combination.

The ratio of the N-hydroxy or N-oxo cyclic imide compound (c2) to the1,2-dicarbonyl compound or its hydroxy reductant (A) is, for example,such that the former (C2)/the latter (A) is from about 0 to about 1, andpreferably from about 0.00001 to about 0.5.

The acylating agent has only to contain at least one compound selectedfrom the metallic compounds (C1) and the N-hydroxy or N-oxo cyclic imidecompounds (C2). Specifically, the embodiments of the acylating agentinclude: (i) an acylating agent composed of the 1,2-dicarbonyl compoundor its hydroxy reductant (A), oxygen (B) and the metallic compound (C1),(ii) an acylating agent composed of the 1,2-dicarbonyl compound or itshydroxy reductant (A), oxygen (B) and the N-hydroxy or N-oxo cyclicimide compound (C2), and (iii) an acylating agent composed of the1,2-dicarbonyl compound or its hydroxy reductant (A), oxygen (B), themetallic compound (C1), and the N-hydroxy or N-oxo cyclic imide compound(C2).

In many cases, the use of an acylating agent containing the metalliccompound (C1) yields a high conversion rate, and the use of an acylatingagent containing the N-hydroxy or N-oxo cyclic imide compound (C2)yields an acyl group-containing compound with high selectivity. Anacylating agent containing the N-hydroxy or N-oxo cyclic imide compound(C2) has a feature that when used in combination with a hydroxyreductant of the 1,2-dicarbonyl compound as the compound (A), thehydroxy reductant is immediately converted into a corresponding1,2-dicarbonyl compound in a system, and an acylation reaction proceedssmoothly.

The acylating agent may further comprise additional components includingradical generators, and radical reaction accelerators in addition to thecomponents (A), (B) and (C). Such additional components include, forinstance, halogens (e.g., chlorine and bromine), peracids (e.g.,peracetic acid and m-chloroperbenzoic acid), and peroxides (e.g.,hydrogen peroxide and hydroperoxide).

Upon production of the bridged cyclic compound containing an acyl grouprepresented by Formula (6), the amount of the 1,2-dicarbonyl compound orits hydroxy reductant (A) is, for example, equal to or more than 1 mole(e.g., from about 1 to about 50 moles), preferably from about 1.5 toabout 20 moles, and more preferably from about 3 to about 10 moles permole of the compound represented by Formula (7). The 1,2-dicarbonylcompound or its hydroxy reductant (A) can also be used as a reactionsolvent.

The amount of oxygen (B) is, usually, equal to or more than 0.5 mole(e.g., equal to or more than 1 mole), preferably from about 1 to about100 moles, and more preferably from about 2 to about 50 moles, per moleof the compound represented by Formula (7). In many cases, excess molesof molecular oxygen to the compound represented by Formula (7) is used.

The amount of the metallic compound (C1) is, for example, from about0.00001 to about 1 mole, and preferably from about 0.0001 to about 0.7mole, per mole of the compound represented by Formula (7). The amount ofthe imide compound (C2) is, for example, from about 0.000001 to about 1mole, preferably from about 0.00001 to about 0.7 mole, per mole of thecompound represented by Formula (7).

A reaction is generally performed in an organic solvent. Such organicsolvents include, but are not limited to, acetic acid, propionic acid,and other organic acids; acetonitrile, propionitrile, benzonitrile, andother nitrites; formamide, acetamide, dimethylformamide (DMF),dimethylacetamide, and other amides; t-butanol, t-amyl alcohol, andother alcohols; hexane, octane, and other aliphatic hydrocarbons;benzene, toluene, and other aromatic hydrocarbons; chloroform,dichloromethane, dichloroethane, carbon tetrachloride, chlorobenzene,trifluoromethylbenzene, and other halogenated hydrocarbons;nitrobenzene, nitromethane, nitroethane, and other nitro compounds;ethyl acetate, butyl acetate, and other esters; diethyl ether,diisopropyl ether, and other ethers; and mixtures of these solvents. Asthe solvent, acetic acid and other organic acids, benzonitrile and othernitrites, trifluoromethylbenzene and other halogenated hydrocarbons arefrequently employed.

A reaction temperature can appropriately be selected with reference tothe types of the reactants and other factors and is, for example, fromabout 0° C. to about 300° C., preferably from about 30° C. to about 250°C., more preferably from about 40° C. to about 200° C., and frequentlyfrom about 40° C. to about 150° C. The reaction can be carried out atambient pressure or under a pressure (under a load).

The reaction can be performed in a batch system, semi-batch system,continuous system or another conventional system, in the presence of, orunder flow of, oxygen. After the completion of the reaction, reactionproducts can be separated and purified according to a procedure such asfiltration, concentration, distillation, extraction, crystallization,recrystallization, column chromatography and other separation means, orany combination of these separation means.

The acylation process using the acylating agent introduces an acyl groupcorresponding to the 1,2-dicarbonyl compound into the bridged cycliccompound represented by Formula (7) predominantly at a bridgeheadposition.

Typical examples of the compounds represented by Formula (6) thusobtained include 1-acetyladamantan-4-one, 1-propionyladamantan-4-one,and other adamantan-4-one derivatives each having an acyl group at the1-position; 6-acetyl-3-oxatricyclo[4.3.1.1^(4,8)]undecan-2-one,6-propionyl-3-oxatricyclo[4.3.1.1^(4,8)]undecan-2-one, and other3-oxatricyclo[4.3.1.1^(4,8)]undecan-2-one derivatives each having anacyl group at the 6-position.

[Compounds Represented by Formula (a1) and Production Thereof]

The compounds represented by Formula (a1) correspond to compoundsrepresented by Formula (a) in which R^(w) is a group containing afluorine atom, and R^(v) is a hydrogen atom or a hydroxyl-protectinggroup. R^(e) in Formula (a1) corresponds to R^(s) in Formula (a)

In Formula (a1), the group containing a fluorine atom in R^(z) includes,but is not limited to, fluorine atom and trifluoromethyl group. Thehydroxyl-protecting group in R^(f) is similar to that in R^(d).

Each of the monomers containing a fluorine atom and having an ethylenicdouble bond represented by Formula (a1) can be produced by allowing thecyclic compound containing an acyl group and having an ethylenic doublebond represented by Formula (f) to react with a fluorine reagent, or bysubjecting the cyclic compound containing an acyl group and having anethylenic double bond represented by Formula (f) to a reaction with afluorine reagent and to a subsequent reaction for introducing aprotecting group.

The symbols in Formula (f) have the same meanings as above. The fluorinereagent is not specifically limited as long as it is a reagent that canintroduce a group containing a fluorine atom into a carbonyl carbonatom. Among such fluorine reagents, trimethyl(trifluoromethyl)silane[TMS-CF₃] and other trifluoromethylating agents and fluorinating agentsare preferred.

A reaction can be performed under a conventional condition withreference to the type of the fluorine reagent. For example, when thetrifluoromethylating agent is used, the reaction is performed in anappropriate solvent such as tetrahydrofuran, preferably in the presenceof a catalyst such as a quaternary ammonium salt. Such quaternaryammonium salts include, for example, tetrabutylammonium fluoride. Areaction temperature is from about −10° C. to about 50° C. The amount ofthe trifluoromethylating agent is, for example, from about 0.9 to about1.5 mole per mole of the compound represented by Formula (f). After thecompletion of the reaction, the resulting reaction mixture is quenched,for example, with dilute hydrochloric acid, and the target compound canbe separated and purified by a separation means such as extraction,distillation, crystallization, recrystallization, or columnchromatography. When the trifluoromethylating agent is used, compoundsrepresented by Formula (a1) in which R^(z) is trifluoromethyl group areobtained under normal conditions.

Compounds represented by Formula (a1) where R^(f) is ahydroxyl-protecting group can be produced by subjecting compounds whereR^(f) is a hydrogen atom, which are obtained according to the aboveprocedure, to a reaction for introducing a protecting group according tothe type of the protecting group. Such reactions for introducing aprotecting group include conventional reactions employed in the field oforganic synthesis.

[Compounds Represented by Formula (12) and Production Thereof]

The compounds represented by Formula (12) are typical examples of themonomers (polymerizable cyclic compounds) containing a fluorine atom andhaving an ethylenic double bond represented by Formula (a1). The symbolsin Formula (12) have the same meanings as those in Formula (a1).

Each of the adamantane derivatives containing a fluorine atom and havingan ethylenic double bond represented by Formula (12) can be produced byallowing the acyladamantane derivative having an ethylenic double bondrepresented by Formula (13) to react with a fluorine reagent, or bysubjecting the acyladamantane derivative having an ethylenic double bondrepresented by Formula (13) to a reaction with a fluorine reagent and toa subsequent reaction for introducing a protecting group.

The fluorine reagent is not specifically limited as long as it is areagent that can introduce a group containing a fluorine atom into acarbonyl carbon atom. Among such fluorine reagents,trimethyl(trifluoromethyl)silane [TMS-CF₃] and othertrifluoromethylating agents are preferred.

A reaction can be performed in the same manner as in the production ofthe compound represented by Formula (1a) from the compound representedby Formula (2). Likewise, the reaction for introducing a protectinggroup into a hydroxyl group can be performed in the same manner asabove.

The acyladamantane derivative having an ethylenic double bondrepresented by Formula (13) can be produced, for example, by allowingthe adamantane derivative having an ethylenic double bond represented byFormula (14) to react with an acylating agent comprising (A1) a1,2-dicarbonyl compound or its hydroxy reductant represented by Formula(15), (B) oxygen, and (C) at least one compound selected from (c1)metallic compounds and (c2) N-hydroxy or N-oxo cyclic imide compounds.

Typical examples of the adamantane derivatives having an ethylenicdouble bond represented by Formula (14) include 1-vinyladamantane,1-(1-propenyl)adamantane, and 1-(1-methylethenyl)adamantane.

The organic groups in R^(e) and R in Formula (15) include similarorganic groups to those mentioned above. Among them, R^(e) is preferablya hydrogen atom, methyl group, ethyl group, or trifluoromethyl group. Z¹and Z² are the same or different and are each an oxygen atom or ahydroxyl group.

In the components (A1), typical examples of the 1,2-dicarbonyl compoundsinclude biacetyl(2,3-butanedione), perfluorobiacetyl, 2,3-pentanedione,3,4-hexanedione, acetylbenzoyl, and other α-diketones. Typical examplesof the hydroxy reductants of the 1,2-dicarbonyl compounds includeacetoin and other α-keto-alcohols; 2,3-butanediol, 2,3-pentanediol, andother vicinal diols.

The components oxygen (B), the metallic compounds (c1), and N-hydroxy orN-oxo cyclic imide compounds (c2) are the same as in the acylatingagents for use in the production of the compounds represented by Formula(6). The acylation reaction can be performed in the same manner as inthe production of the compounds represented by Formula (6).

Among the compounds represented by Formula (13), compounds (aldehydes)in which R^(e) is a hydrogen atom can also be produced by reducingcorresponding carboxylic acids according to a conventional procedure.

Typical examples of the adamantane derivatives containing a fluorineatom and having an ethylenic double bond represented by Formula (12)include

-   1-(1-trifluoromethyl-1-hydroxyethyl)-3-vinyladamantane,-   1-(1-trifluoromethyl-1-hydroxymethyl)-3-vinyladamantane, and-   1-[1,1-bis(trifluoromethyl)-1-hydroxymethyl]-3-vinyladaman tane.    [Compounds Represented by Formula (16)]

The compounds represented by Formula (16) are examples of compoundsrepresented by Formulae (b), (b1), (c), and (c1) in which R^(a) or R^(b)is combined with a carbon atom constituting ring A² or with a carbonatom constituting ring A³ to form a condensed ring.

Z, R^(x), and R^(y) in Formula (16) have the same meanings as above.Each of the compounds represented by Formula (16) can be produced byusing a norbornene derivative or an 2-oxabicyclo[3.2.1^(1,5)]-6-octenederivative as a starting material according to a procedure similar tothe production of the compounds represented by Formula (1).

Typical examples of the compounds represented by Formula (16) include

-   5-trifluoromethyl-5-hydroxybicyclo[2.2.1]-2-heptene, and    3,3-difluoro-2-oxabicyclo[3.2.1^(1,5)]-6-octene.

[Compounds Represented by Formula (17)]

The compounds represented by Formula (17) are typical examples ofcompounds represented by Formulae (a) and (a1) in which R^(a) or R^(b)is combined with a carbon atom constituting ring A¹ to form a condensedring.

R^(e), R^(f), and R^(z) in Formula (17) have the same meanings asdefined above. Each of the compounds represented by Formula (17) can beproduced by using a norbornene derivative as a starting material in thesame manner as in the production of the compounds represented by Formula(12).

Typical examples of the compounds represented by Formula (17) include

-   5-(1-trifluoromethyl-1-hydroxymethyl)bicyclo[2.2.1]-2-heptene,-   5-(1-trifluoromethyl-1-hydroxyethyl)bicyclo[2.2.1]-2-heptene,-   5-(1-trifluoromethyl-1-trimethylsilyloxyethyl)bicyclo[2.2.1]-2-heptene,-   5-[1-trifluoromethyl-1-(1-ethoxyethyloxy)ethyl]bicyclo[2.2.1]-2-heptene,-   5-[1,1-bis(trifluoromethyl)-1-hydroxymethyl]bicyclo[2.2.1]-2-heptene,    and-   5-(1-trifluoromethyl-1-hydroxy-1-(norborn-2-yl)methyl)bicyclo[2.2.1]-2-heptene.

[Compounds Represented by Formula (g1) and Production Thereof]

The compounds represented by Formula (g1) correspond to compoundsrepresented by Formula (g) in which R^(w) is a group containing afluorine atom and R^(v) is a hydrogen atom or a hydroxyl-protectinggroup. R^(e) in Formula (g1) corresponds to R^(s) in Formula (g).

In Formula (g1), the group containing a fluorine atom in R^(z) includes,for example, fluorine atom and trifluoromethyl group. Thehydroxyl-protecting group in R^(f) is similar to that in R^(d).

Each of the compounds containing a fluorine atom and having an ethylenicdouble bond represented by Formula (g1) can be produced by allowing thecyclic compound containing an acyl group and having an ethylenic doublebond represented by Formula (k) to react with a fluorine reagent, or bysubjecting the cyclic compound containing an acyl group and having anethylenic double bond represented by Formula (k) to a reaction with afluorine reagent and to a subsequent reaction for introducing aprotecting group.

The symbols in Formula (k) have the same meanings as above. The fluorinereagent is not specifically limited as long as it is a reagent that canintroduce a group containing a fluorine atom into a carbonyl carbonatom. Among such fluorine reagents, trimethyl(trifluoromethyl)silane[TMS-CF₃] and other trifluoromethylating agents and fluorinating agentsare preferred.

A reaction can be performed under a conventional condition withreference to the type of the fluorine reagent. For example, when atrifluoromethylating agent is used, the reaction is performed in anappropriate solvent such as tetrahydrofuran, preferably in the presenceof a catalyst such as a quaternary ammonium salt. Such quaternaryammonium salts include, for example, tetrabutylammonium fluoride. Areaction temperature is from about −10° C. to about 50° C. The amount ofthe trifluoromethylating agent is, for example, from about 0.9 to about1.5 mole per mole of the compound represented by Formula (k). After thecompletion of the reaction, the resulting reaction mixture is quenched,for example, with dilute hydrochloric acid, and the target compound canbe separated and purified by a separation means such as extraction,distillation, crystallization, recrystallization, or columnchromatography. When the trifluoromethylating agent is used, compoundsrepresented by Formula (g1) in which R^(z) is a trifluoromethyl groupare obtained under normal conditions.

Compounds represented by Formula (g1) where R^(f) is ahydroxyl-protecting group can be produced by subjecting compounds whereR^(f) is a hydrogen atom, which are obtained according to the aboveprocedure, to a reaction for introducing a protecting group according tothe type of the protecting group. Such reactions for introducing aprotecting group include conventional reactions employed in the field oforganic synthesis.

[Compounds Represented by Formula (g2) and Production Thereof]

The compounds represented by Formula (g2) correspond to compoundsrepresented by Formula (g) in which R^(s) and R^(w) are groupscontaining a fluorine atom, R^(v) is a hydrogen atom or ahydroxyl-protecting group, and W² is an oxygen atom or a sulfur atom.

In Formula (g2), the group containing a fluorine atom in R^(w5)includes, for example, fluorine atom and trifluoromethyl group. Thehydroxyl-protecting group in R^(f) is similar to that in R^(d).

Each of the monomers containing a fluorine atom and having an ethylenicdouble bond represented by Formula (g2) can be produced by allowing thecyclic compound containing a hydroxyl group or mercapto group and havingan ethylenic double bond represented by Formula (1) to react with thecarbonyl compound containing a fluorine atom represented by Formula (m),or by subjecting the cyclic compound containing a hydroxyl group ormercapto group and having an ethylenic double bond represented byFormula (1) to a reaction with the carbonyl compound containing afluorine atom represented by Formula (m) and to a subsequent reactionfor introducing a protecting group.

In Formula (1), W^(2a) is an oxygen atom or a sulfur atom, and the othersymbols have the same meanings as above. The group containing a fluorineatom in R^(w5) in Formula (m) is similar to that in R^(x). A typicalexample of the carbonyl compounds containing a fluorine atom representedby Formula (m) is hexafluoroacetone.

The reaction between the cyclic compound containing a hydroxyl group ormercapto group and having an ethylenic double bond represented byFormula (1) and the carbonyl compound containing a fluorine atomrepresented by Formula (m) is performed under an appropriate conditionwith reference to the types of the reaction materials and other factors.For example, a reaction temperature is from about −10° C. to about 50°C. The amount of the carbonyl compound containing a fluorine atomrepresented by Formula (m) is from about 0.9 to about 1.5 moles per moleof the compound represented by Formula (1). The reaction yields acorresponding monomer containing an electron-withdrawing grouprepresented by Formula (g2).

Compounds represented by Formula (g2) where R^(f) is ahydroxyl-protecting group can be produced by subjecting compounds whereR^(f) is a hydrogen atom, which are obtained according to the aboveprocedure, to a reaction for introducing a protecting group according tothe type of the protecting group. Such reactions for introducing aprotecting group include conventional reactions employed in the field oforganic synthesis.

[Compounds Represented by Formula (18) and Others]

The compounds represented by Formula (18) are typical examples ofcompounds represented by Formula (g1) in which R^(a) or R^(b) iscombined with a carbon atom constituting ring A⁴ to form a condensedring. The symbols in Formula (18) have the same meanings as above. Thecompounds represented by Formula (18) can be produced according to asimilar process to that in the production of the compounds representedby Formula (g1) or in the production of the compounds represented byFormula (g2).

Typical examples of the compounds represented by Formula (18) include

-   5-[1,1-bis(trifluoromethyl)-1-hydroxymethyl]oxybicyclo[2.2.1]-2-heptene,-   5-[1,1-bis(trifluoromethyl)-1-hydroxymethyl]oxymethylbicyclo[2.2.1]-2-heptene,    and-   5-hydroxy-6-[1,1-bis(trifluoromethyl)-1-hydroxymethyl]oxybicyclo[2.2.1]-2-heptene.

In the present invention, compounds corresponding to the compoundsrepresented by Formula (18) in which the bicyclo[2.2.1]-2-heptene ring(bicyclo[2.2.1]-2-hepten-5-yl group) is replaced by a 1-vinyladamantanering (1-vinyladamant-3-yl group) are also preferred. These compoundscorrespond to compounds represented by Formula (g1) in which W¹ is asingle bond and ring A⁴ is an adamantane ring. They can be produced in asimilar process to that in the production of the compounds representedby Formula (g1) or in the production of the compounds represented byFormula (g2). Typical examples of the compounds in question include

-   1-[1,1,-bis(trifluoromethyl)-1-hydroxymethyl]oxy-3-vinyladamantane    and-   1-[1,1-bis(trifluoromethyl)-1-hydroxymethyl]oxymethyl-3-vinyladamantane.

[Compounds Represented by Formula (h1) and Production Thereof]

The compounds represented by Formula (h1) correspond to compoundsrepresented by Formula (h) in which the two R^(w2) s are groupscontaining a fluorine atom. The groups containing a fluorine atom inR^(x) and R^(y1) in Formula (h1) include, for example, fluorine atom andtrifluoromethyl group.

Each of the monomers containing a fluorine atom and having an ethylenicdouble bond represented by Formula (h1) can be produced by allowing thecyclic compound containing a thiocarbonyl group and having an ethylenicdouble bond represented by Formula (n) to react with a fluorine reagent.The symbols in Formula (n) have the same meanings as above. As thefluorine reagent, those mentioned above can be used. A reaction can beperformed in a conventional condition with reference to the type of thefluorine reagent. When a fluorinating agent is used as the fluorinereagent, the reaction is performed in an appropriate solvent such asmethylene chloride at a temperature of from about −70° C. to about 50°C. The amount of the fluorinating agent is from about 0.9 to about 5moles per mole of the compound represented by Formula (n). After thecompletion of the reaction, the target compound can be separated andpurified by a separation means such as extraction, distillation,crystallization, recrystallization, or column chromatography. When thefluorinating agent is used, compounds represented by Formula (h1) inwhich R^(x) and R^(y1) are fluorine atoms are obtained under normalconditions.

[Compounds Represented by Formula (19)]

The compounds represented by Formula (19) are typical examples ofcompounds represented by Formula (h1) in which R^(a) or R^(b) iscombined with a carbon atom constituting ring A⁵ to form a condensedring. The symbols in Formula (19) have the same meanings as above. Thecompounds represented by Formula (19) can be produced in the same manneras in the production of the compounds represented by Formula (h1).

Typical examples of the compounds represented by Formula (19) include

-   8,8-difluoro-7,9-dithiatricyclo[4.3.0.1^(2,5)]-3-decene,-   8,8-difluoro-7,9-dioxatricyclo[4.3.0.1^(2,5)]-3-decene, and-   8,8-bis(trifluoromethyl)-7,9-dioxatricyclo[4.3.0.1^(2,5)]-3-decene.

[Compounds Represented by Formula (20)]

The compounds represented by Formula (20) are typical examples ofcompounds represented by Formula (h1) in which R^(a) or R^(b) iscombined with a carbon atom constituting ring A⁵ to form a condensedring and G² is a single bond, or compounds represented by Formula (c1)in which R^(a) or R^(b) is combined with a carbon atom constituting ringA³ to form a condensed ring. The symbols in Formula (20) have the samemeanings as above. The compounds represented by Formula (20) can beproduced in the same manner as in the production of the compoundsrepresented by Formula (h1) or in the production of the compoundsrepresented by Formula (c1).

Typical examples of the compounds represented by Formula (20) include

-   7,7-difluoro-8-thiatricyclo[4.3.0.1^(2,5)]-3-decene,-   7,7,9,9-tetrafluoro-8-thiatricyclo[4.3.0.1^(2,5)]-3-decene,-   7,7-difluoro-8-oxatricyclo[4.3.0.1^(2,5)]-3-decene, and-   7,7,9,9-tetrafluoro-8-oxatricyclo[4.3.0.1^(2,5)]-3-decene.

[Compounds Represented by Formula (i1) and Production Thereof]

The compounds represented by Formula (i1) correspond to compoundsrepresented by Formula (i) in which the two R^(w3)s are groupscontaining a fluorine atom. In Formula (i1), the groups containing afluorine atom in R^(x) and R^(y1) include, for example, fluorine atomand trifluoromethyl group.

Each of the monomers containing a fluorine atom and having an ethylenicdouble bond represented by Formula (i1) can be produced by allowing thecyclic compound containing a thiocarbonyl group and having an ethylenicdouble bond represented by Formula (o) to react with a fluorine reagent.The symbols in Formula (o) have the same meanings as above. As thefluorine reagent, those mentioned above can be used. A reaction can beperformed in a conventional condition with reference to the type of thefluorine reagent. When a fluorinating agent is used as the fluorinereagent, the reaction is performed in an appropriate solvent such asmethylene chloride at a temperature of from about −70° C. to about 50°C. The amount of the fluorinating agent is from about 0.9 to about 5moles per mole of the compound represented by Formula (o). After thecompletion of the reaction, the target compound can be separated andpurified by a separation means such as extraction, distillation,crystallization, recrystallization, or column chromatography. When thefluorinating agent is used, compounds represented by Formula (i1) inwhich R^(x) and R^(y1) are fluorine atoms are obtained under normalconditions.

[Compounds Represented by Formula (j1) and Production Thereof]

The compounds represented by Formula (j1) correspond to compoundsrepresented by Formula (j) in which all the four R^(w4)s are groupscontaining a fluorine atom. In Formula (j1), the groups containing afluorine atom in R^(x) and R^(y1) include, for example, fluorine atomand trifluoromethyl group.

Each of the monomers containing a fluorine atom and having an ethylenicdouble bond represented by Formula (j1) can be produced by allowing thecyclic compound containing a thiocarbonyl group and having an ethylenicdouble bond represented by Formula (p) to react with a fluorine reagent.The symbols in Formula (p) have the same meanings as defined above. Asthe fluorine reagent, those mentioned above can be used. A reaction canbe performed in a conventional condition with reference to the type ofthe fluorine reagent. For example, when a fluorinating agent is used asthe fluorine reagent, the reaction is performed in an appropriatesolvent such as methylene chloride at a temperature of from about −70°C. to about 50° C. The amount of the fluorinating agent is from about0.9 to about 5 moles per mole of the compound represented by Formula(p). After the completion of the reaction, the target compound can beseparated and purified by a separation means such as extraction,distillation, crystallization, recrystallization, or columnchromatography. When the fluorinating agent is used, compoundsrepresented by Formula (j1) in which R^(x) and R^(y1) are fluorine atomsare obtained under normal conditions.

[Compounds Represented by Formula (21)]

The compounds represented by Formula (21) are typical examples ofcompounds represented by Formula (i1) in which m1=m2=0. The symbols inFormula (21) have the same meanings as defined above. The compoundsrepresented by Formula (21) can be produced in the same manner as in theproduction of the compounds represented by Formula (i1).

Typical examples of the compounds represented by Formula (21) include2,2-difluoro-1,3-dioxolene and 2,2-difluoro-1,3-dithiolene.

[Compounds Represented by Formula (22)]

The compounds represented by Formula (22) are typical examples ofcompounds represented by Formula (j1) in which m1=m2=0. The symbols inFormula (22) have the same meanings as above. The compounds representedby Formula (22) can be produced in the same manner as in the productionof the compounds represented by Formula (j1).

Typical examples of the compounds represented by Formula (22) include2,2,5,5-tetrafluoro-1-oxolene and 2,2,5,5-tetrafluoro-1-thiolene.

[Compounds in Which W¹ is an Ester Bond]

Each of the compounds represented by Formulae (a), (b), (c), (g), and(h) in which W¹ is an ester bond can be produced by preparing a compoundof Formula (a), (b), (c), (g), or (h) in which a hydroxyl group isbonded instead of W¹ in the same manner as in the production of thecompound represented by Formula (a), (b), (c), (g), or (h), and allowingthe resulting compound to react with a carboxylic acid having apolymerizable unsaturated group, such as (meth) acrylic acid, or itsreactive derivative. Conventional esterification reactions can beapplied to this reaction.

The monomers of the present invention each preferably have a molecularweight of less than or equal to 800 (e.g., from about 80 to about 800),and more preferably less than or equal to 500 (e.g., from about 80 toabout 500).

[Polymeric Compounds for Use in Photoresists]

The polymeric compounds for use in photoresists of the present inventioninclude polymers each containing at least one of constitutionalrepeating units represented by Formula (G), (H), (I) or (J). The symbolsin these formulae have the same meanings as in corresponding Formula(g), (h), (i) or (j). The polymeric compounds for use in photoresists ofthe present invention each contain an electron-withdrawing group such asa fluorine atom, have a specific cyclic structure and can thereby yieldvery high sensitivity in patterning.

Each of the polymeric compounds for use in photoresists of the presentinvention can be produced by subjecting one or more monomers representedby Formula (g), (h), (i) or (j) corresponding to each constitutionalrepeating unit and where necessary additional copolymerizable compoundsto a polymerization reaction. Such additional copolymerizable compoundscan appropriately be selected from acrylic monomers, olefinic monomers(including cyclic olefinic monomers), and other polymerizable compoundswith reference to desired functions. Such acrylic monomers include, butare not limited to, 2-trifluoromethylacrylic acid or its esters (e.g.,t-butyl 2-trifluoromethylacrylate), and fluorinated alkyl esters of(meth)acrylic acid. The olefinic monomers include, but are not limitedto, norbornene and norbornene derivatives each having a group containinga fluorine atom (including a fluorine atom itself) combined to its ring.Polymerization can be performed according to a conventional procedurefor use in the production of olefinic polymers or acrylic polymers, suchas solution polymerization or melt polymerization.

In addition, preferred polymeric compounds for use in photoresists alsoinclude polymers obtained by (co-)polymerizing at least one selectedfrom the monomers containing an electron-withdrawing group representedby Formula (a), the monomers containing an electron-withdrawing grouprepresented by Formula (b), the monomers containing anelectron-withdrawing group represented by Formula (c), the monomershaving a cyclic thioester skeleton represented by Formula (e), theadamantanone derivatives having an ethylenic double bond represented byFormula (2), the 3-oxatricyclo[4.3.1.1^(4,8)]undecane derivatives havingan ethylenic double bond represented by Formula (3), and theacyladamantane derivatives having an ethylenic double bond representedby Formula (13) or by copolymerizing at least one of these monomers andan additional polymerizable compound. Such additional polymerizablecompounds include similar compounds mentioned above. Polymerization canbe performed according to a conventional procedure for use in theproduction of olefinic polymers or acrylic polymers, such as solutionpolymerization or melt polymerization.

[Photosensitive Resin Compositions, Patterning Process and Process forManufacturing Semiconductors]

The photosensitive resin compositions of the present invention eachcontain at least the polymeric compound for use in photoresists and aphotosensitive acid generator.

Such photosensitive acid generators include conventional or knowncompounds that efficiently generate an acid upon irradiation with light.Such compounds include, but are not limited to, diazonium salts,iodonium salts (e.g., diphenyliodoniumhexafluorophosphate), sulfoniumsalts (e.g., triphenylsulfonium hexafluoroantimonate, triphenylsulfoniumhexafluorophosphate, and triphenylsulfonium methanesulfonate), sulfonicacid esters [e.g.,1-phenyl-1-(4-methylphenyl)sulfonyloxy-1-benzoylmethane,1,2,3-trisulfonyloxymethylbenzene,1,3-dinitro-2-(4-phenylsulfonyloxymethyl)benzene, and1-phenyl-1-(4-methylphenylsulfonyloxymethyl)-1-hydroxy-1-benzoylmethane], oxathiazol derivatives, s-triazine derivatives,disulfone derivatives (e.g., diphenyldisulfone), imide compounds, oximesulfonates, diazonaphthoquinone, and benzointosylate. Each of thesephotosensitive acid generators can be used alone or in combination.

The amount of the photosensitive acid generator can appropriately beselected depending on the strength of the acid generated by lightirradiation, the proportions of the individual constitutional repeatingunits in the polymeric compound and is, for example, from about 0.1 toabout 30 parts by weight, preferably from about 1 to about 25 parts byweight, and more preferably from about 2 to 20 parts by weight, relativeto 100 parts by weight of the polymeric compound for use inphotoresists.

The photosensitive resin composition may further comprise additionalcomponents. Such additional components include, but are not limited to,alkali-soluble resins (e.g., novolak resins, phenol resins, imideresins, and carboxyl-group-containing resins), and other alkali-solublecomponents, coloring agents (e.g., dyestuffs), and organic solvents(e.g., hydrocarbons, halogenated hydrocarbons, alcohols, esters, amides,ketones, ethers, Cellosolves, Carbitols, glycol ether esters, andmixtures of these solvents) The patterning process of the presentinvention comprises at least the steps of applying the photosensitiveresin composition to a substrate, applying light with a wavelength ofless than or equal to 220 nm, baking, and developing. For example, thephotosensitive resin composition is applied to a base or a substrate, isdried, and the resulting film (resist film) is exposed to light througha predetermined mask (or is further subjected to post-exposure baking)to form a latent image pattern, and the film is then developed, forexample, by alkali aqueous solution and is selectively dissolved andremoved the exposed part or the unexposed part to highly precisely yielda fine pattern.

Such substrates include, for example, silicon wafers, metals, plastics,glasses, and ceramics. The photoresist resin composition can be appliedusing a conventional application means such as a spin coater, a dipcoater, and a roller coater. The applied film has a thickness of, forexample, about 0.1 to about 20 μm, and preferably about 0.3 to about 2μm.

Light rays with different wavelengths such as ultraviolet rays andX-rays can be applied. For example, g-line, i-line, and excimer laser(e.g., XeCl, KrF, KrCl, ArF, ArCl, or F₂ excimer laser) are usually usedfor semiconductor resists. Preferred wavelengths of these light sourcesare less than or equal to 220 nm (e.g., from 130 to 220 nm). Thephotosensitive resin composition of the present invention isspecifically suitable for irradiation with F₂ laser light. An exposureenergy is, for example, about 1 to about 1000 mJ/cm², and preferablyabout 10 to about 500 mJ/cm².

The process for producing a semiconductor of the present inventioncomprises at least the step of patterning according to the abovepatterning process. For example, a resist is patterned by the patterningprocess, and the substrate is etched by using the patterned resist as anetching mask to thereby yield a semiconductor (an electronic part).

INDUSTRIAL APPLICABILITY

The present invention provides novel monomers each having a cyclicskeleton and carrying an electron-withdrawing group and a polymerizablegroup, as well as processes for efficiently producing the same. Thesecompounds can be used as monomers for functional polymers such asphotoresist transparent polymeric compounds for use in photosensitiveresin compositions.

The present invention also provides intermediates that are useful forthe production of the monomers each having a cyclic skeleton andcarrying an electron-withdrawing group and a polymerizable group, aswell as processes for efficiently producing the same.

In addition, the polymeric compounds for use in photoresists,photosensitive resin composition, patterning process and process forproducing a semiconductor according to the present invention can formvery fine patterns with high precision, for example, using F₂ laser.

EXAMPLES

The present invention will be illustrated in further detail withreference to several examples below, which are not intended to limit thescope of the invention.

Example 1 Production of6-acetyl-3-oxatricyclo[4.3.1.1^(4,8)]undecan-2-one

In a flask were placed 3-oxatricyclo[4.3.1.1^(4,8)]undecan-2-one (16.6g, 100 mmol), acetylacetonatocobalt [Co(acac)₂] (50 mmol),2,3-butanedione (600 mmol), and acetic acid (100 g). A condenser and anoxygen balloon were attached to the flask, and the mixture in the flaskwas vigorously stirred at 80° C. for 4 hours. After the completion ofthe reaction, the reaction mixture was concentrated, followed byaddition of toluene and washing with water. The resulting organic layerwas concentrated, the concentrate was subjected to silica gel columnchromatography and thereby yielded the title compound6-acetyl-3-oxatricyclo[4.3.1.1^(4,8)]undecan-2-one in a yield of 37%.

[Spectral Data]

MS m/e: 209 ([M⁺]), 171, 121.

Example 2 Production of6-(1-hydroxyethyl)-3-oxatricyclo[4.3.1.1^(4,8)]undecan-2-one

In a flask was placed 6-acetyl-3-oxatricyclo[4.3.1.1^(4,8)]undecan-2-one(20.8 g, 100 mmol) obtained by the procedure of Example 1, was treatedwith methanol (40 ml) and 0.1 N aqueous sodium hydroxide solution (6ml), followed by gradual addition of sodium borohydride (NaBH₄) (50mmol) and stirring for 30 minutes. After the completion of the reaction,the reaction mixture was neutralized with 1 N hydrochloric acid, wasextracted with ethyl acetate, the organic layer was concentrated andthereby yielded the title compound6-(1-hydroxyethyl)-3-oxatricyclo[4.3.1.1^(4,8)]undecan-2-one in a yieldof 97%.

[Spectral Data]

MS m/e: 210 ([M⁺]), 165.

Example 3 Production of6-vinyl-3-oxatricyclo[4.3.1.1^(4,8)]undecan-2-one

In a flask were placed6-(1-hydroxyethyl)-3-oxatricyclo[4.3.1.1^(4,8)]undecan-2-one (21.0 g,100 mmol) obtained by the procedure of Example 2, sulfuric acid (10mmol), hydroquinone (21 mg), and toluene (200 g), and the resultingmixture was stirred for 4 hours under dehydration and reflux. After thecompletion of the reaction, the reaction mixture was washed with water,the organic layer was concentrated, the concentrate was subjected tosilica gel column chromatography and thereby yielded the title compound6-vinyl-3-oxatricyclo[4.3.1.1^(4,8)]undecan-2-one in a yield of 62%.

[Spectral Data]

MS m/e: 193 ([M⁺]), 155, 121.

Example 4 Production of6-vinyl-3-oxatricyclo[4.3.1.1^(4,8)]undecane-2-thione

To a mixture of 6-vinyl-3-oxatricyclo[4.3.1.1^(4,8)]undecan-2-one (10mmol) obtained by the procedure of Example 3 and toluene (50 ml) wasadded 2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane 2,4-disulfide[(p-MeO-C₆H₄P(═S)—S—)₂)] (10 mmol), and the resulting mixture wasstirred at 110° C. for 24 hours. The reaction mixture was concentrated,the concentrate was subjected to silica gel column chromatography andthereby yielded the title compound6-vinyl-3-oxatricyclo[4.3.1.1^(4,8)]undecane-2-thione in a yield of 75%.

[Spectral Data]

MS m/e: 209 ([M⁺]), 182, 177, 121.

Example 5 Production of2,2-difluoro-6-vinyl-3-oxatricyclo[4.3.1.1_(4,8)]undecane

To a mixture of 6-vinyl-3-oxatricyclo[4.3.1.1^(4,8)]undecane-2-thione (2mmol) obtained by the procedure of Example 4 and dry methylene chloride(10 ml) was added a solution of diethylaminosulfur trifluoride (DAST) inmethylene chloride (1 M solution, 4 ml, 2 equivalents) using a syringeat room temperature in an atmosphere of nitrogen gas, followed bystirring for 24 hours. After the completion of the reaction, theresulting mixture was washed with an aqueous sodium hydrogen carbonatesolution, and the organic layer was concentrated. The concentrate wassubjected to silica gel column chromatography and thereby yielded thetitle compound 2,2-difluoro-6-vinyl-3-oxatricyclo[4.3.1.1^(4,8)]undecanein a yield of 52%.

[Spectral Data]

MS m/e: 231 ([M⁺]), 204, 188.

Example 6 Production of 1-acetyladamantan-4-one

In a flask were placed 2-adamantanone (100 mmol), acetylacetonatocobalt[Co(acac)₂] (50 mmol), 2,3-butanedione (600 mmol), and acetic acid (100g). A condenser and an oxygen balloon were attached to the flask, andthe mixture in the flask was vigorously stirred at 80° C. for 4 hours.After the completion of the reaction, the reaction mixture wasconcentrated, was diluted with toluene and washing with water. Theresulting organic layer was concentrated, the concentrate was subjectedto silica gel column chromatography and thereby yielded the titlecompound 1-acetyladamantan-4-one in a yield of 21%.

[Spectral Data]

¹H-NMR (CDCl₃, TMS) δ: 2.4-1.5 (m, 13H), 2.1 (s, 3H).

MS m/e: 193 ([M⁺]), 149, 121, 93, 79.

Example 7 Production of 1-(1-hydroxyethyl)adamantan-4-one

In a flask was placed 1-acetyladamantan-4-one (100 mmol) obtained by theprocedure of Example 6 and was treated with methanol (40 ml) and 0.1 Naqueous sodium hydroxide solution (6 ml), followed by gradual additionof sodium borohydride (NaBH₄) (50 mmol) and stirring for 30 minutes.After the completion of the reaction, the reaction mixture wasneutralized with 1 N hydrochloric acid, was extracted with ethylacetate, the organic layer was concentrated and thereby yielded thetitle compound 1-(1-hydroxyethyl) adamantan-4-one in a yield of 52%.

[Spectral Data]

¹H-NMR (CDCl₃, TMS) δ: 3.3 (m, 1H), 2.4-1.4 (m, 14H), 1.1 (s, 3H).

MS m/e: 195 ([M⁺]), 149.

Example 8 Production of 1-vinyladamantan-4-one

In a flask were placed 1-(1-hydroxyethyl)adamantan-4-one (100 mmol)obtained by the procedure of Example 7, sulfuric acid (10 mmol),hydroquinone (21 mg), and toluene (200 g), followed by stirring for 4hours under dehydration and reflux. After the completion of thereaction, the reaction mixture was washed with water, the resultingorganic layer was concentrated, the concentrate was subjected to silicagel column chromatography and thereby yielded the title compound1-vinyladamantan-4-one in a yield of 78%.

[Spectral Data]

¹H-NMR (CDCl₃, TMS) δ: 5.7 (dd, 1H), 4.9-4.8 (m, 2H), 2.4-1.5 (m, 13H).

MS m/e: 177 ([M⁺]), 161, 121.

Example 9 Production of 4-trifluoromethyl-4-hydroxy-1-vinyladamantane

In tetrahydrofuran (THF) (30 ml) were dissolved 1-vinyladamantan-4-one(10 mmol) obtained by the procedure of Example 8 andtrimethyl(trifluoromethyl)silane [TMS-CF₃] (12 mmol). The resultingsolution was treated with 1M solution of tetrabutylammonium fluoride inTHF (0.2 ml) at 0° C. with stirring. After its yellow color disappeared,the reaction mixture was stirred at room temperature for 24 hours. Themixture was then treated with 1N hydrochloric acid for 20 hours withstirring. The reaction mixture was concentrated, the concentrate wassubjected to silica gel column chromatography and thereby yielded thetitle compound 4-trifluoromethyl-4-hydroxy-1-vinyladamantane in a yieldof 54%.

[Spectral Data]

MS m/e: 247 ([M⁺]), 178, 68.

¹⁹F-NMR (CDCl₃) δ: −76.0.

Example 10 Production of1-(1-trifluoromethyl-1-hydroxyethyl)-3-vinyladamantane

In a flask were placed 1-vinyladamantane (100 mmol),acetylacetonatocobalt [Co (acac)₂] (50 mmol), 2,3-butanedione (600mmol), and acetic acid (100 g). A condenser and an oxygen balloon wereattached to the flask, and the mixture in the flask was vigorouslystirred at 80° C. for 4 hours. After the completion of the reaction, thereaction mixture was concentrated, was diluted with toluene and waswashed with water. The resulting organic layer was concentrated, theconcentrate was subjected to silica gel column chromatography andthereby yielded 1-acetyl-3-vinyladamantane in a yield of 36%.

[Spectral Data of 1-acetyl-3-vinyladamantane]

MS m/e: 205 ([M⁺]), 152, 131.

In tetrahydrofuran (THF) (30 ml) were dissolved1-acetyl-3-vinyladamantane (10 mmol) obtained by the above procedure andtrimethyl(trifluoromethyl)silane [TMS-CF₃] (12 mmol). The resultingsolution was treated with 1M solution of tetrabutylammonium fluoride inTHF (0.2 ml) at 0° C. with stirring. After its yellow color disappeared,the reaction mixture was further stirred at room temperature for 24hours. The mixture was then treated with 1N hydrochloric acid for 20hours with stirring. The reaction mixture was concentrated, theconcentrate was subjected to silica gel column chromatography andthereby yielded the title compound1-(1-trifluoromethyl-1-hydroxyethyl)-3-vinyladamantane in a yield of71%.

[Spectral Data]

MS m/e: 275 ([M⁺]), 152, 68.

Example 11 Production of5-(1-trifluoromethyl-1-hydroxymethyl)bicyclo[2.2.1]-2-heptene

According to the following reaction formula,5-(1-trifluoromethyl-1-hydroxymethyl)bicyclo[2.2.1]-2-heptene wasproduced.

Initially, 5-formylbicyclo[2.2.1]-2-heptene (Formula (23), 10 mmol) andtrimethyl(trifluoromethyl)silane [TMS-CF₃] (12 mmol) were dissolved intetrahydrofuran (THF) (30 ml). The resulting solution was treated with1M solution of tetrabutylammonium fluoride in THF (0.2 ml) at 0° C. withstirring. After its yellow color disappeared, the reaction mixture wasfurther stirred at room temperature for 2 hours. The mixture was thentreated with 1N hydrochloric acid for 20 hours with stirring. Thereaction mixture was concentrated, the concentrate was subjected tosilica gel column chromatography and thereby yielded5-(1-trifluoromethyl-1-hydroxymethyl)bicyclo[2.2.1]-2-heptenerepresented by Formula (24) in a yield of 73%.

[Spectral Data]

MS m/e: 193 ([M⁺]), 175, 68.

Example 12 Production of5-trifluoromethyl-5-hydroxybicyclo[2.2.1]-2-heptene

According to the following reaction formula,5-trifluoromethyl-5-hydroxybicyclo[2.2.1]-2-heptene was produced.

Initially, 5-oxobicyclo[2.2.1]-2-heptene (Formula (25), 10 mmol) andtrimethyl(trifluoromethyl)silane [TMS-CF₃] (12 mmol) were dissolved intetrahydrofuran (THF) (30 ml). The resulting solution was treated with1M solution of tetrabutylammonium fluoride in THF (0.2 ml) at 0° C. withstirring. After its yellow color disappeared, the reaction mixture wasfurther stirred at room temperature for 24 hours. The mixture was thentreated with 1N hydrochloric acid for 20 hours with stirring. Thereaction mixture was concentrated, the concentrate was subjected tosilica gel column chromatography and thereby yielded5-trifluoromethyl-5-hydroxybicyclo[2.2.1]-2-heptene represented byFormula (26) in a yield of 48%.

[Spectral Data]

MS m/e: 179 ([M⁺]), 161, 68.

Example 13 [Production of7,7-difluoro-4-methacryloyloxy-6-oxatricyclo[3.2.1.1^(3,8)]nonane

According to the following reaction formula,7,7-difluoro-4-methacryloyloxy-6-oxatricyclo[3.2.1.1^(3,8)]nonanerepresented by Formula (30) was produced.

To a mixture of 4-hydroxy-6-oxatricyclo[3.2.1.1^(3,8)]nonan-7-onerepresented by Formula (27) (10 mmol) and toluene (50 ml) was added2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane 2,4-disulfide[(p-MeO-C₆H₄P(═S)—S—)₂)] (10 mmol), and the resulting mixture wasstirred at 110° C. for 24 hours. The reaction mixture was concentrated,the concentrate was subjected to silica gel column chromatography andthereby yielded 4-hydroxy-6-oxatricyclo[3.2.1.1^(3,8)]nonane-7-thionerepresented by Formula (28) in a yield of 65%.

[Spectral Data of the Compound of Formula (28)]

MS m/e: 171 ([M⁺]), 152, 120.

To a mixture of the cyclic thioester derivative represented by Formula(28) (2 mmol) obtained by the above procedure and dry methylene chloride(10 ml) was added a solution of diethylaminosulfur trifluoride (DAST) inmethylene chloride (1 M solution, 4 ml, 2 equivalents) using a syringeat room temperature in an atmosphere of nitrogen gas, followed bystirring for 24 hours. After the completion of the reaction, theresulting mixture was washed with an aqueous sodium hydrogencarbonatesolution, and the organic layer was concentrated. The concentrate wassubjected to silica gel column chromatography and thereby yielded7,7-difluoro-4-hydroxy-6-oxatricyclo[3.2.1.1^(3,8)]nonane represented byFormula (29) in a yield of 59%.

[Spectral Data of the Compound of Formula (29)]

MS m/e: 177 ([M⁺]), 159, 141.

A mixture of the cyclic compound having a group containing a fluorineatom represented by Formula (29) (10 mmol) obtained by the aboveprocedure, methacrylic acid (20 mmol), concentrated sulfuric acid (0.5mmol), toluene (8 folds by volume that of the above three components),and hydroquinone (10000 ppm) was stirred for 8 hours under dehydrationand reflux. After the completion of the reaction, the reaction mixturewas concentrated, the concentrate was subjected to silica gel columnchromatography and thereby yielded7,7-difluoro-4-methacryloyioxy-6-oxatricyclo[3.2.1.1^(3,8)]nonanerepresented by Formula (30) in a yield of 82%.

[Spectral Data of the Compound of Formula (30)]

MS m/e: 245 ([M⁺]) 160, 69.

Example 14 Production of5-[1,1-bis(trifluoromethyl)-1-hydroxymethyl]oxybicyclo[2.2.1]-2-heptene

According to the following reaction formula,5-[1,1-bis(trifluoromethyl)-1-hydroxymethyl]oxybicyclo[2.2.1]-2-heptenewas produced.

In a reactor equipped with a dry ice-ethanol reflux condenser was placed5-hydroxybicyclo[2.2.1]-2-heptene (Formula (31), 50 mmol), andhexafluoroacetone gas (50 mmol) was blown thereinto while cooling on anice bath. The resulting mixture was stirred at room temperature forfurther 1 hour and thereby yielded5-[1,1-bis(trifluoromethyl)-1-hydroxymethyl]oxybicyclo[2.2.1]-2-heptenerepresented by Formula (32) in a yield of 95%.

[Spectral Data]

MS m/e: 277 (M+1), 259, 66.

¹⁹F-NMR (CDCl₃) δ: −79.7.

Example 15 Production of5-[1,1-bis(trifluoromethyl)-1-hydroxymethyl]oxymethylbicyclo[2.2.1]-2-heptene

According to the following reaction formula,5-[1,1-bis(trifluoromethyl)-1-hydroxymethyl]oxymethylbicyclo[2.2.1]-2-heptenewas produced.

In a reactor equipped with a dry ice-ethanol reflux condenser was placed5-hydroxymethylbicyclo[2.2.1]-2-heptene (Formula (33), 30 mmol), andhexafluoroacetone gas (30 mmol) was blown thereinto while cooling on anice bath. The resulting mixture was stirred at room temperature forfurther 1 hour and thereby yielded5-[1,1-bis(trifluoromethyl)-1-hydroxymethyl]oxymethylbicyclo[2.2.1]-2-heptenerepresented by Formula (34) in a yield of 97%.

[Spectral Data]

MS m/e: 291 (M+1), 273, 66.

Example 16 Production of5-hydroxy-6-[1,1-bis(trifluoromethyl)-1-hydroxymethyl]oxybicyclo[2.2.1]-2-heptene]

According to the following reaction formula,5-hydroxy-6-[1,1-bis(trifluoromethyl)-1-hydroxymethyl]oxybicyclo[2.2.1]-2-heptenewas produced.

In a reactor equipped with a dry ice-ethanol reflux condenser was placed5,6-dihydroxybicyclo[2.2.1]-2-heptene (Formula (35), 30 mmol), andhexafluoroacetone gas (30 mmol) was blown thereinto while cooling on anice bath. The resulting mixture was stirred at room temperature forfurther 0.5 hour, the reaction mixture was subjected to silica gelcolumn chromatography and thereby yielded5-hydroxy-6-[1,1-bis(trifluoromethyl)-1-hydroxymethyl]oxybicyclo[2.2.1]-2-heptenerepresented by Formula (36) in a yield of 38%.

[Spectral Data]

MS m/e: 293 (M+1), 275, 68.

Example 17 Production of 2,2-difluoro-1,3-dioxolene

According to the following reaction formula, 2,2-difluoro-1,3-dioxolenerepresented by Formula (39) was produced.

To a mixture of 1,3-dioxolen-2-one represented by Formula (37) (50 mmol)and toluene (50 ml) was added2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane 2,4-disulfide[(p-MeO-C₆H₄P(═S)—S—)₂)] (50 mmol), and the resulting mixture wasstirred at 110° C. for 24 hours. The reaction mixture was concentrated,the concentrate was subjected to silica gel column chromatography andthereby yielded 1,3-dioxolene-2-thione represented by Formula (38) in ayield of 72%.

[Spectral Data of the Compound of Formula (38)]

MS m/e: 277 (M+1), 259, 66.

¹H-NMR (CDCl₃) δ: 6.62 (d, 2H).

To a mixture of the cyclic compound represented by Formula (38) (20mmol) obtained by the above procedure and dry methylene chloride (30 ml)was added a solution of diethylaminosulfur trifluoride (DAST) inmethylene chloride (1 M solution, 2 equivalents) at room temperature inan atmosphere of nitrogen gas, followed by stirring for 24 hours. Afterthe completion of the reaction, the resulting mixture was washed with anaqueous sodium hydrogen carbonate solution, and the organic layer wasconcentrated. The concentrate was subjected to silica gel columnchromatography and thereby yielded 2,2-difiuoro-1,3-dioxolenerepresented by Formula (39) in a yield of 58%.

[Spectral Data of the Compound of Formula (39)]

MS m/e: 109 (M+1).

Example 18 Production of 2,2,5,5-tetrafluoro-1-oxolene

According to the following reaction formula,2,2,5,5-tetrafluoro-1-oxolene represented by Formula (42) was produced.

To a mixture of maleic anhydride represented by Formula (40) (50 mmol)and toluene (30 ml) was added2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane 2,4-disulfide[(p-MeO-C₆H₄P(═S)—S—)₂)] (50 mmol), and the resulting mixture wasstirred at 110° C. for 24 hours. The reaction mixture was concentrated,the concentrate was subjected to silica gel column chromatography andthereby yielded 1-oxolene-2,5-dithione represented by Formula (41) in ayield of 21%.

[Spectral Data of the Compound of Formula (41)]

MS m/e: 131 (M+1).

To a mixture of the cyclic compound represented by Formula (41) obtainedby the above procedure (5 mmol) and dry methylene chloride (10 ml) wasadded a solution of diethylaminosulfur trifluoride (DAST) in methylenechloride (1 M solution, 4 equivalents) at room temperature in anatmosphere of nitrogen gas, followed by stirring for 24 hours. After thecompletion of the reaction, the resulting mixture was washed with anaqueous sodium hydrogencarbonate solution, and the organic layer wasconcentrated. The concentrate was subjected to silica gel columnchromatography and thereby yielded 2,2,5,5-tetrafluoro-1-oxolenerepresented by Formula (42) in a yield of 48%.

[Spectral Data of the Compound of Formula (42)]

MS m/e: 143 (M+1).

Example 19 Production of 2,2-difluoro-1,3-dithiolene

According to the following reaction formula, 2,2-difluoro-1,3-dithiolenerepresented by Formula (44) was produced.

To a mixture of 1,3-dithiolene-2-thione (30 mmol) and dry methylenechloride (30 ml) was added a solution of diethylaminosulfur trifluoride(DAST) in methylene chloride (1 M solution, 2 equivalents) at roomtemperature in an atmosphere of nitrogen gas, followed by stirring for24 hours. After the completion of the reaction, the resulting mixturewas washed with an aqueous sodium hydrogencarbonate solution, and theorganic layer was concentrated. The concentrate was subjected to silicagel column chromatography and thereby yielded2,2-difluoro-1,3-dithiolene represented by Formula (44) in a yield of37%.

[Spectral Data of the Compound of Formula (44)]

MS m/e: 141 (M+1).

¹H-NMR (CDCl₃) δ: 6.67 (d, 2H).

Example 20 Production of8,8-difluoro-7,9-dithiatricyclo[4.3.0.1^(2,5)]-3-decene

According to the following reaction formula,8,8-difluoro-7,9-dithiatricyclo[4.3.0.1^(2,5)]-3-decene represented byFormula (46) was produced.

To a mixture of 7,9-dithiatricyclo[4.3.0.1^(2,5)]-3-decene-8-thionerepresented by Formula (45) (10 mmol) and dry methylene chloride (20 ml)was added a solution of diethylaminosulfur trifluoride (DAST) inmethylene chloride (1 M solution, 2 equivalents) at room temperature inan atmosphere of nitrogen gas, followed by stirring for 24 hours. Afterthe completion of the reaction, the resulting mixture was washed with anaqueous sodium hydrogencarbonate solution, and the organic layer wasconcentrated. The concentrate was subjected to silica gel columnchromatography and thereby yielded8,8-difluoro-7,9-dithiatricyclo[4.3.0.1^(2,5)]-3-decene represented byFormula (46) in a yield of 67%.

[Spectral Data of the Compound of Formula (46)]

MS m/e: 207 (M+1), 66.

Example 21 Production of5-[1-trifluoromethyl-1-hydroxy-1-(norborn-2-yl)methyl]bicyclo[2.2.1]-2-heptene

According to the following reaction formula,5-[1-trifluoromethyl-1-hydroxy-1-(norborn-2-yl)methyl]bicyclo[2.2.1]-2-heptenewas produced.

A mixture of 5-(norborn-2-ylcarbonyl)bicyclo[2.2.1]-2-heptene (Formula(47), 10 mmol), trimethyl(trifluoromethyl)silane [TMS-CF₃] (12 mmol),and dry tetrahydrofuran (THF) (20 ml) was treated with a 1-M solution oftetrabutylammonium fluoride in THF (0.05 equivalent) in an atmosphere ofnitrogen gas for 2 hours while cooling on ice bath and stirring, and theresulting mixture was stirred at room temperature for further 20 hours.The mixture was treated with 1 N hydrochloric acid with stirring for 20hours. The reaction mixture was concentrated, the concentrate wassubjected to silica gel column chromatography and thereby yielded5-[1-trifluoromethyl-1-hydroxy-1-(norborn-2-yl)methyl]bicyclo[2.2.1]-2-heptenerepresented by Formula (48) in a yield of 87%.

[Spectral Data]

MS m/e: 289 (M+1), 271, 69.

Example 22 Production of5-(1-trifluoromethyl-1-hydroxyethyl)bicyclo[2.2.1]-2-heptene and5-(1-trifluoromethyl-1-trimethylsilyloxyethyl)bicyclo[2.2.1]-2-heptene

According to the following reaction formula,5-(1-trifluoromethyl-1-hydroxyethyl)bicyclo[2.2.1]-2-heptene and5-(1-trifluoromethyl-1-trimethylsilyloxyethyl)bicyclo[2.2.1]-2-heptenewere produced. In the formula, TMS represents a trimethylsilyl group.

A mixture of 5-acetylbicyclo[2.2.1]-2-heptene (Formula (49), 50 mmol),trimethyl(trifluoromethyl)silane [TMS-CF₃] (60 mmol), and drytetrahydrofuran (THF) (100 ml) was treated with a 1-M solution oftetrabutylammonium fluoride in THF (0.05 equivalent) in an atmosphere ofnitrogen gas for 2 hours while cooling on ice bath and stirring, and theresulting mixture was stirred at room temperature for further 20 hours.The reaction mixture was concentrated, the concentrate was subjected tosilica gel column chromatography and thereby yielded5-(1-trifluoromethyl-1-hydroxyethyl)bicyclo[2.2.1]-2-heptene representedby Formula (50) in a yield of 5% and5-(1-trifluoromethyl-1-trimethylsilyloxyethyl)bicyclo[2.2. 1]-2-heptenerepresented by Formula (51) in a yield of 81%.

A solution of the above-prepared5-(1-trifluoromethyl-1-trimethylsilyloxyethyl)bicyclo[2.2. 1]-2-heptenerepresented by Formula (51) (35 mmol) in acetone (50 ml) was treatedwith 3 N hydrochloric acid with stirring for 20 hours. The reactionmixture was concentrated, the concentrate was subjected to silica gelcolumn chromatography and thereby yielded5-(1-trifluoromethyl-1-hydroxyethyl)bicyclo[2.2.1]-2-heptene representedby Formula (50) in a yield of 93%.

[Spectral Data of the Compound of Formula (50)]

MS m/e: 207 (M+1), 189, 163, 66.

¹⁹F-NMR (CDCl₃) δ: −81.8.

¹H-NMR (CDCl₃) δ: 6.28 (dd, 1H), 6.08 (dd, 1H), 3.03 (brs, 1H), 2.88(brs, 1H), 2.52 (m, 1H), 1.93 (m, 1H), 1.83 (s, 1H), 1.50-1.20 (m, 6H).

[Spectral Data of the Compound of Formula (51)]

MS m/e: 279 (M+1), 263, 189, 167, 66.

Example 23 Production of5-[1-trifluoromethyl-1-(1-ethoxyethyloxy)ethyl]bicyclo[2.2.1]-2-heptene]

According to the following reaction formula,5-[1-trifluoromethyl-1-(1-ethoxyethyloxy)ethyl]bicyclo[2.2.1]-2-heptenewas produced.

A mixture of5-(1-trifluoromethyl-1-hydroxyethyl)bicyclo[2.2.1]-2-heptene representedby Formula (50) obtained in Example 22 (20 mmol), ethyl vinyl ether (22mmol) and methylene chloride (50 ml) was treated with p-toluenesulfonicacid (0.4 mmol) at room temperature for 5 hours with stirring. Thereaction mixture was washed with an aqueous sodium hydrogencarbonatesolution, the organic layer was concentrated, the concentrate wassubjected to silica gel column chromatography and thereby yielded5-[1-trifluoromethyl-1-(1-ethoxyethyloxy)ethyl]bicyclo[2.2.1]-2-heptenerepresented by Formula (52) in a yield of 87%.

[Spectral Data]

MS m/e: 315 (M+1), 225, 66.

Example 24 Synthesis of a Polymer having the Following Structure

In a 100-ml egg plant type flask equipped with a reflux condenser wereplaced5-[1,1-bis(trifluoromethyl)-1-hydroxymethyl]oxabicyclo[2.2.1]-2-heptenerepresented by Formula (32) (21 mmol), t-butyl 2-trifluoromethylacrylate(9 mmol), and dry tetrahydrofuran (25 ml), and the resulting mixture wastreated with AIBN (2,2′-azobisisobutyronitrile) (500 mg) at atemperature of 60° C. to 65° C. in an atmosphere of argon gas for 2hours with stirring. After standing to cool, the reaction mixture waspoured onto methanol, the deposited precipitate was collected byfiltration, was then subjected to the precipitation and purificationprocedure again and thereby yielded the target polymer in a yield of43%. The polymerization ratio in the polymer was determined based on thesignal ratio in ¹H-NMR and was found to be 70:30 as shown in thestructural formula. The polymer had a weight average molecular weight of10700 in terms of polystyrene and a molecular weight distribution(Mw/Mn) of 2.25 as determined by GPC analysis.

Example 25 Synthesis of a Polymer Having the Following Structure

In a 100-ml egg plant type flask equipped with a reflux condenser wereplaced5-[1,1-bis(trifluoromethyl)-1-hydroxymethyl]oxabicyclo[2.2.1]-2-heptenerepresented by Formula (32) (9 mmol), t-butyl 2-trifluoromethylacrylate(21 mmol), and dry tetrahydrofuran (25 ml), and the resulting mixturewas treated with AIBN (2,2′-azobisisobutyronitrile) (500 mg) at 60° C.to 65° C. in an atmosphere of argon gas for 2 hours with stirring. Afterstanding to cool, the reaction mixture was poured onto methanol, thedeposited precipitate was collected by filtration, was then subjected tothe precipitation and purification procedure and thereby yielded thetarget polymer in a yield of 53%. The polymerization ratio in thepolymer was determined based on the signal ratio in ¹H-NMR and was foundto be 30:70 as shown in the structural formula. The polymer had a weightaverage molecular weight of 11800 in terms of polystyrene as determinedby GPC analysis.

Example 26 Synthesis of a Polymer having the Following Structure

In a 100-ml egg plant type flask equipped with a reflux condenser wereplaced 2,2-difluoro-1,3-dioxolene represented by Formula (39) (15 mmol),t-butyl 2-trifluoromethylacrylate (15 mmol), and dry tetrahydrofuran (25ml), and the resulting mixture was treated with AIBN(2,2′-azobisisobutyronitrile) (500 mg) at a temperature of 60° C. to 65°C. in an atmosphere of argon gas for 2 hours with stirring. Afterstanding to cool, the reaction mixture was poured onto methanol, thedeposited precipitate was collected by filtration, was then subjected tothe precipitation and purification procedure again and thereby yieldedthe target polymer in a yield of 41%. The polymerization ratio in thepolymer was determined based on the signal ratio in ¹H-NMR and was foundto be 49:51 as shown in the structural formula. The polymer had a weightaverage molecular weight of 9600 in terms of polystyrene and a molecularweight distribution (Mw/Mn) of 1.92 as determined by GPC analysis.

Example 27 Synthesis of a Polymer having the Following Structure

In a 100-ml egg plant type flask equipped with a reflux condenser wereplaced 8,8-difluoro-7,9-dithiatricyclo[4.3.0.1^(2,5)]-3-decenerepresented by Formula (46) (15 mmol), t-butyl 2-trifluoromethylacrylate(15 mmol), and dry tetrahydrofuran (25 ml), and the resulting mixturewas treated with AIBN (2,2′-azobisisobutyronitrile) (500 mg) at atemperature of 60° C. to 65° C. in an atmosphere of argon gas for 2hours with stirring. After standing to cool, the reaction mixture waspoured onto methanol, the deposited precipitate was collected byfiltration, was then subjected to the precipitation and purificationprocedure again and thereby yielded the target polymer in a yield of51%. The polymerization ratio in the polymer was determined based on thesignal ratio in ¹H-NMR and was found to be 50:50 as shown in thestructural formula. The polymer had a weight average molecular weight of9600 in terms of polystyrene and a molecular weight distribution (Mw/Mn)of 1.79 as determined by GPC analysis.

Example 28 Synthesis of a Polymer having the Following Structure

In a 100-ml egg plant type flask equipped with a reflux condenser wereplaced5-[1,1-bis(trifluoromethyl)-1-hydroxymethyl]oxybicyclo[2.2.1]-2-heptenerepresented by Formula (32) (30 mmol) and dry tetrahydrofuran (25 ml),and the resulting mixture was treated with AIBN(2,2′-azobisisobutyronitrile) (500 mg) at a temperature of 60° C. to 65°C. in an atmosphere of argon gas for 2 hours with stirring. Afterstanding to cool, the reaction mixture was poured onto methanol, thedeposited precipitate was collected by filtration, was then subjected tothe precipitation and purification procedure again and thereby yieldedthe target polymer in a yield of 51%.

TEST EXAMPLE Determination of Pattering by a Resist Using the Polymer

A resist (a photosensitive resin composition) having the followingcomposition was prepared.

(a) Polymer (Example 1): 100 parts by weight

(b) Triphenylsulfonium trifluoromethanesulfonate: 2 parts by weight

(c) Additive (triethanolamine): 0.1 part by weight

The above components (a), (b), and (c) were dissolved in 2000 parts byweight of propylene glycol monomethyl ether monoacetate, the resultingsolution was filtrated through a membrane filter having a pore size of0.1 μm and thereby yielded a resist. The resist was applied to an 4-inchsilicon substrate by spin coating, was dried on a hot plate at 90° C.for 90 seconds and thereby yielded a resist layer 0.4 μm thick. Theresist layer was irradiated with ArF excimer laser light through a maskusing an exposure system. The exposed resist layer was then immediatelyheated at 110° C. for 90 seconds, was developed by dipping in a 2.38% byweight tetramethylammonium hydroxide aqueous solution for 60 seconds,was subsequently rinsed with pure water for 60 seconds and therebyyielded a positive resist pattern. In this procedure, the exposure atwhich a 0.20-μm line-and-space pattern was obtained was 9 mJ/cm².

1. A monomer containing an electron-withdrawing group, represented byfollowing Formula (b) or (c):

wherein A², and A³ are each a ring; R^(a), R^(b), R^(c), and R^(u) arethe same or different and are each a hydrogen atom or an organic group;at least one of R^(t) and R^(w1), and at least one of the two R^(w2)sare each an electron-withdrawing group, and the others are each ahydrogen atom or an organic group; W¹ is a single bond or a linkagegroup; and n denotes an integer of from 2 to 25, where at least two ofR^(a), R^(b), R^(c), R^(t), R^(u), R^(w1), R^(w2), W¹, carbon atomsconstituting ring A², and carbon atoms constituting ring A³ may becombined to form a ring, respectively.
 2. The monomer containing anelectron-withdrawing group according to claim 1, wherein theelectron-withdrawing groups in R^(t), R^(w1), and R^(w2) are groupcontaining a fluorine atom.
 3. The monomer containing anelectron-withdrawing group according to claim 1, wherein ring A² or ringA³ is a monocyclic ring or bridged ring containing at least a 5- to7-membered carbocyclic ring or oxygen-containing heterocyclic ring. 4.The monomer containing an electron-withdrawing group according to claim1, having a bridged ring skeleton, the bridged ring skeleton includingring A² or ring A³ and containing 7 to 15 carbon atoms.
 5. A process forproducing a monomer containing an electron-withdrawing group, theprocess comprising the step of allowing a cyclic ketone having anethylenic double bond, represented by following Formula (d):

wherein A² is a ring; R^(a), R^(b), R^(c) and R^(u) are the same ordifferent and are each a hydrogen atom or an organic group; W¹ is asingle bond or a linkage group; and n denotes an integer of from 2 to25, where at least two of R^(a), R^(b), R^(c), R^(u), W¹, and carbonatoms constituting ring A² may be combined to form a ring, respectively,to react with a fluorine reagent, or subjecting the cyclic ketone havingan ethylenic double bond represented by Formula (d) to a reaction withthe fluorine reagent and to a subsequent reaction for introducing aprotecting group to thereby yield a monomer containing a fluorine atomand having an ethylenic double bond, represented by following Formula(b1):

wherein R^(x) is a group containing a fluorine atom; R^(d) is a hydrogenatom or a hydroxyl-protecting group; A², R^(a), R^(b), R^(c), R^(u), W¹,and n have the same meanings as defined above, where at least two ofR^(a), R^(b), R^(c), R^(u), W¹, and carbon atoms constituting ring A²may be combined to form a ring, respectively.
 6. A process for producinga monomer containing an electron-withdrawing group, the processcomprising the step of allowing a cyclic thioester having an ethylenicdouble bond, represented by following Formula (e):

wherein A³ is a ring; R^(a), R^(b), R^(c), and R^(u) are the same ordifferent and are each a hydrogen atom or an organic group; W¹ is asingle bond or a linkage group; and n denotes an integer of from 2 to25, where at least two of R^(a), R^(b), R^(c), R^(u), W¹, and carbonatoms constituting ring A³ may be combined to form a ring, respectively,to react with a fluorine reagent to thereby yield a monomer containing afluorine atom and having an ethylenic double bond, represented byfollowing Formula (c1):

wherein R^(x) and R^(y1) are each a group containing a fluorine atom;A³, R^(a), R^(b), R^(c), R^(u), W¹, and n have the same meanings asdefined above, where at least two of R^(a), R^(b), R^(c), R^(u), W¹, andcarbon atoms constituting ring A³ may be combined to form a ring,respectively.
 7. A process for producing a monomer containing anelectron-withdrawing group, the process comprising the step of allowinga cyclic compound containing an acyl group and having an ethylenicdouble bond, represented by following Formula (f):

wherein A¹ is a ring; R^(a), R^(b), R^(c), and R^(e) are the same ordifferent and are each a hydrogen atom or an organic group; W¹ is asingle bond or a linkage group, where at least two of R^(a), R^(b),R^(c), R^(e), W¹, and carbon atoms constituting ring A¹ may be combinedto form a ring, respectively, to react with a fluorine reagent, orsubjecting the cyclic compound containing an acyl group and having anethylenic double bond represented by Formula (f) to a reaction with thefluorine reagent and to a subsequent reaction for introducing aprotecting group to thereby yield a monomer containing a fluorine atomand having an ethylenic double bond, represented by following Formula(a1):

wherein R^(z) is a group containing a fluorine atom; R^(f) is a hydrogenatom or a hydroxyl-protecting group; and A¹, R^(a), R^(b), R^(c), R^(e),and W¹ have the same meanings as defined above, where at least two ofR^(a), R^(b), R^(c), R^(e), W¹, and carbon atoms constituting ring A¹may be combined to form a ring, respectively.
 8. A monomer containing anelectron-withdrawing group, represented by following Formula (a):

wherein A¹ is a ring; R^(a), R^(b), and R^(c) are the same or differentand are each a hydrogen atom or an organic group; at least one of R^(s),R^(w) and R^(v) is an electron-withdrawing group, and the others areeach a hydrogen atom or an organic group; W¹ is a single bond or alinkage group; where at least two of R^(a), R^(b), R^(c), R^(s), R^(v),R^(w), W¹, carbon atoms constituting ring A¹ may be combined to form aring, respectively; with the proviso that when at least one of thecarbon atoms constituting ring A¹ are combined with R^(a) or R^(b) toform a ring, then R^(v) is at least one selected from the groupconsisting of a hydrogen, a hydrocarbon group, a heterocyclic group, analkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, a cyanogroup, and a nitro group, wherein the heterocyclic group is substitutedor unsubstituted, and wherein the hydrocarbon group is unsubstituted oris substituted by at least on substituent selected from a groupconsisting of oxo group, hydroxyl group which may be protected by aprotecting group, hydroxymethyl group which may be protected by aprotecting group, amino group which may be protected by a protectinggroup, carboxyl group which may be protected by a protecting group,substituted oxycarbonyl group, substituted or unsubstituted carbamoylgroup, nitro group, acyl group, cyano group, aryl group, and aheterocyclic group.
 9. A monomer containing an electron-withdrawinggroup, represented by following Formula (a):

wherein A¹ is a ring; R^(a), R^(b), and R^(c) are the same or differentand are each a hydrogen atom or an organic group; a least one of R^(s)and R^(w) is an electron-withdrawing group, a hydrogen atom or anorganic group; R^(v) is an electron-withdrawing group; W¹ is a singlebond or a linkage group; where at least two of R^(c), R^(s), R^(v),R^(w), W¹, carbon atoms constituting ring A¹ may be combined to form aring, respectively.
 10. The monomer containing an electron-withdrawinggroup according to claim 8 or 9, wherein the electron-withdrawing groupsin R^(s), R^(v), and R^(w), are group containing a fluorine atom. 11.The monomer containing an electron-withdrawing group according to claim8 or 9, wherein ring A¹ is a monocyclic ring or bridged ring containingat least a 5- to 7-membered carbocyclic ring or oxygen-containingheterocyclic ring.
 12. The monomer containing an electron-withdrawinggroup according to claim 8 or 9, having a bridged ring skeleton, thebridged ring skeleton including ring A¹ and containing 7 to 15 carbonatoms.